Polymer compound, net-like polymer compound produced by crosslinking the polymer compound, composition for organic electroluminescence element, organic electroluminescence element, organic EL display, and organic EL lighting

ABSTRACT

An object of the invention is to provide a polymer compound having a high hole transport capacity, excellent in electrochemical stability, and suitable to film formation according to a wet film formation method. Another object of the invention is to provide an organic electroluminescence element having a high current efficiency, a low drive voltage, and a long derive lifetime. The polymer compound has a crosslinking group bonding to the arylamine moiety in the repeating unit via at least one single bond therebetween.

CROSS REFERENCE TO RELATED APPLICATION

This application is a Continuation application of U.S. application Ser.No. 12/936,136, filed on Jan. 24, 2011, which is a 371 ofPCT/JP09/056,829, filed on Apr. 1, 2009, and claims priority to thefollowing applications: Japanese Patent Application No. 2008-096522,filed on Apr. 2, 2008.

TECHNICAL FIELD

The present invention relates to a polymer compound having acrosslinking group and capable of forming a film according to a wet filmformation method, to a net-like polymer compound produced bycrosslinking the polymer compound, to a composition for organicelectroluminescence elements that contains the polymer compound, to anorganic electroluminescence element having a layer that contains thenet-like polymer compound, having a high current efficiency andexcellent in drive stability, and to an organic EL display and anorganic EL lighting equipped with the device.

BACKGROUND ART

Recently, an electroluminescence element comprising an organic thin film(organic electroluminescence element) has been developed. For forming anorganic thin film in an organic electroluminescence element, there arementioned a vacuum evaporation method and a wet film formation method.

The vacuum evaporation method facilitates lamination, therefore havingthe advantages in that it improves charge injection from anode and/orcathode and facilitates exciton containment in light emission layer. Thewet film formation method has the advantages in that it does not requirea vacuum process and facilitates large-area film formation andfacilitates incorporation of plural materials having different functionsin one layer (coating liquid).

However, lamination is difficult in the wet film formation method, andtherefore the method is inferior to the vacuum evaporation method indrive stability, and at present, it is not as yet on a practicable levelexcept some cases. In particular, the wet film formation method mayenable two-layer lamination using an organic solvent and a water-basesolvent, but three-layer or more multi-layer lamination is difficult inthe method.

To solve the problems with lamination, Patent Reference 1 has proposed apolymer compound having a crosslinking group and having repeating units(III-1) and (III-2) mentioned below, and discloses a lamination methodin which the reaction of the crosslinking group makes the compoundinsoluble in organic solvent.

However, the polymer compound described in Patent Reference 1 has acrosslinking group at the 9-position of the fluorene ring thereof, andis therefore poor in electrochemical stability, especially in resistanceto reduction (electron); and it is considered that the drive stabilityof the organic electroluminescence element comprising the polymercompound described in Patent Reference 1 may be insufficient.

Patent References 2 and 3 disclose polymer compounds each having arepeating unit represented by the formula mentioned below; however, incase where these compounds are used in producing devices, there occursome problems in that flat films could not be formed and the drivelifetime of the devices to be obtained is short.

PRIOR ART REFERENCES Patent References

-   Patent Reference 1: JP-T 2004-505169-   Patent Reference 2: WO2008/038747-   Patent Reference 3: WO2005/053056

Problems that the Invention is to Solve

An object of the invention is to provide a polymer compound having ahigh hole transport capacity, excellent in electrochemical stability,and suitable to film formation according to a wet film formation method.

Another object of the invention is to provide an organicelectroluminescence element having a high current efficiency, a lowdrive voltage, and a long derive lifetime.

Means for Solving the Problems

The present inventors have assiduously studied for the purpose ofsolving the above-mentioned problems and, as a result, have found thatthe polymer compound having a specific repeating unit mentioned belowhas high electrochemical stability and high hole transport performanceand is suitable to a wet film formation method where layer lamination iseasy, and have reached the present invention.

Specifically, the invention includes the following features.

The invention is directed to a polymer compound having a repeating unitrepresented by the following formula (I) (hereinafter this is referredto as “polymer compound (i) of the invention”):

(In the formula, R¹ and R² each independently represent a hydrogen atom,an aromatic hydrocarbon group optionally having a substituent, anaromatic heterocyclic group optionally having a substituent, or an alkylgroup optionally having a substituent, R¹ and R² may bond to each otherto form a ring;

n indicates an integer of from 0 to 3;

Ar¹ and Ar² each independently represent a direct bond, an aromatichydrocarbon group optionally having a substituent, or an aromaticheterocyclic group optionally having a substituent;

Ar³ to Ar⁵ each independently represent an aromatic hydrocarbon groupoptionally having a substituent, or an aromatic heterocyclic groupoptionally having a substituent.

T represents a group containing a crosslinking group. However, when Ar¹,Ar² and Ar⁴ are fluorene rings, then they do not have a group containinga crosslinking group as the substituent.)

Preferably, the above polymer compound (i) further contains a repeatingunit represented by the following formula (I′):

(In the formula, R¹¹ and R¹² each independently represent a hydrogenatom, an aromatic hydrocarbon group optionally having a substituent, anaromatic heterocyclic group optionally having a substituent, or an alkylgroup optionally having a substituent, R¹¹ and R¹² may bond to eachother to form a ring;

m indicates an integer of from 0 to 3;

Ar¹¹ and Ar¹² each independently represent a direct bond, an aromatichydrocarbon group optionally having a substituent, or an aromaticheterocyclic group optionally having a substituent;

Ar¹³ to Ar¹⁵ each independently represent an aromatic hydrocarbon groupoptionally having a substituent, or an aromatic heterocyclic groupoptionally having a substituent.

However, R¹¹ and R¹², and Ar¹¹ to Ar¹⁵ do not have a crosslinking groupas the substituent.)

In the above polymer compound (i), preferably, the crosslinking group isselected from a group of the following crosslinking groups T′:

<Group of Crosslinking Groups T′>

(In the formulae, R²¹ to R²⁵ each independently represent a hydrogenatom or an alkyl group. Ar⁴¹ represents an aromatic hydrocarbon groupoptionally having a substituent, or an aromatic heterocyclic groupoptionally having a substituent.

The benzocyclobutene ring may have a substituent.

The substituents may together form a ring.)

The invention is also directed to a polymer compound having a repeatingunit represented by the following formula (II) (hereinafter this isreferred to as “polymer compound (ii) of the invention”):

(In the formula, p indicates an integer of from 0 to 3;

Ar²¹ and Ar²² each independently represent a direct bond, an aromatichydrocarbon group optionally having a substituent, or an aromaticheterocyclic group optionally having a substituent;

Ar²³ to Ar²⁵ each independently represent an aromatic hydrocarbon groupoptionally having a substituent, or an aromatic heterocyclic groupoptionally having a substituent;

T² represents a group containing a group represented by the followingformula (IV).

However, Ar²¹ and Ar²² are not direct bonds at the same time.

Further, when Ar²¹, Ar²² and Ar²⁴ are fluorene rings, they do not have agroup containing a crosslinking group as the substituent.)

(The benzocyclobutene ring in the formula (IV) may have a substituent.The substituents may bond to each other to form a ring.)

Preferably, the polymer compound (ii) further contains a repeating unitrepresented by the following formula (II′):

(In the formula (II′), q indicates an integer of from 0 to 3;

Ar³¹ and Ar³² each independently represent a direct bond, an aromatichydrocarbon group optionally having a substituent, or an aromaticheterocyclic group optionally having a substituent;

Ar³³ to Ar³⁵ each independently represent an aromatic hydrocarbon groupoptionally having a substituent, or an aromatic heterocyclic groupoptionally having a substituent.

However, Ar³¹ and Ar³² are not direct bonds at the same time.

Ar³¹ to Ar³⁵ do not have a group containing a group of the formula (IV)as the substituent.

Further, when Ar³¹, Ar³² and Ar³⁴ are fluorene rings, they do not have agroup containing a crosslinking group as the substituent.)

The invention is also directed to a polymer compound having at least onerepeating unit selected from a group of the following repeating units A,and at least one repeating unit selected from a group of the followingrepeating units B.

<Group of Repeating Units A>

<Group of Repeating Units B>

The invention is also directed to a net-like polymer compound, acomposition for organic electroluminescence element, an organicelectroluminescence element, as well as to an organic EL display and anorganic EL lighting.

A net-like polymer compound produced by crosslinking the polymercompound of the invention.

A composition for organic electroluminescence element, containing thepolymer compound of the invention.

An organic electroluminescence element having, on a substrate, an anode,a cathode and an organic layer between the anode and the cathode,wherein the organic layer has a layer containing the net-like polymercompound of the invention.

The organic electroluminescence element wherein the layer containing thenet-like polymer compound is a hole injection layer or a hole transportlayer.

The organic electroluminescence element wherein the organic layer has ahole injection layer, a hole transport layer and a light emission layer,and all the hole injection layer, the hole transport layer and the lightemission layer are formed according to a wet film formation method.

An organic EL display comprising the organic electroluminescence elementof the invention.

An organic EL lighting comprising the organic electroluminescenceelement of the invention.

Hereinafter the “polymer compound of the invention” is meant to indicateboth the “polymer compound (i) of the invention” and the “polymercompound (ii) of the invention”.

Advantage of the Invention

The polymer compound of the invention has a high hole transport capacityand has a sufficient solubility in solvent, and may increase surfacesmoothness in film formation. Accordingly, an organicelectroluminescence element that has a layer containing a net-likepolymer compound produced by crosslinking the polymer compound of theinvention (hereinafter this may be referred to as “crosslinked layer”)can be driven at a low voltage and has a high light emission efficiency,high heat resistance and a long drive lifetime.

Further, the polymer compound of the invention is excellent inelectrochemical stability, film formability, charge transferability,light emission capability and heat resistance, and is thereforeapplicable to a hole-injecting material, a hole-transporting material, alight-emitting material, a host material, an electron-injectingmaterial, an electron-transporting material and the like, in accordancewith the layer constitution of devices.

BRIEF DESCRIPTION OF THE DRAWING

FIG. 1 This is a cross-sectional view graphically showing one example ofthe structure of the organic electroluminescence element of theinvention.

MODE FOR CARRYING OUT THE INVENTION

Embodiments of the invention are described in detail hereinunder,however, the description of the constitutive features given below is forsome examples (typical examples) of embodiments of the invention, andthe invention should not be limited to these contents, not oversteppingthe scope and the spirit thereof.

<1. Polymer Compound (i)>

The polymer compound (i) of the invention is a polymer compoundcontaining a repeating unit of the following formula (I):

(In the formula, R¹ and R² each independently represent a hydrogen atom,an aromatic hydrocarbon group optionally having a substituent, anaromatic heterocyclic group optionally having a substituent, or an alkylgroup optionally having a substituent, R¹ and R² may bond to each otherto form a ring;

n indicates an integer of from 0 to 3;

Ar¹ and Ar² each independently represent a direct bond, an aromatichydrocarbon group optionally having a substituent, or an aromaticheterocyclic group optionally having a substituent;

Ar³ to Ar⁵ each independently represent an aromatic hydrocarbon groupoptionally having a substituent, or an aromatic heterocyclic groupoptionally having a substituent.

T represents a group containing a crosslinking group.

However, when Ar¹, Ar² and Ar⁴ are fluorene rings, then they do not havea group containing a crosslinking group as the substituent.)

[1-1. Structural Characteristics]

The polymer compound (i) of the invention has a group that contains atleast one crosslinking group in one molecule as the substituent, andtherefore its film formed according to a wet film formation method canbe made insoluble in organic solvent under a mild condition.

The fluorene ring in the main chain strongly participates in chargetransfer with expanding HOMO (highest occupied molecular orbital) andLUMO (lowest unoccupied molecular orbital) thereof.

The polymer compound (i) of the invention does not have a groupcontaining a crosslinking group in the fluorene ring in the main chain,and is therefore excellent in electrochemical stability, especially inreduction resistance stability. In addition, the compound has acrosslinking group bonding to the arylamine moiety via at least onesingle bond therebetween, and is therefore excellent in oxidationresistance.

[1-2. Ar¹ to Ar⁵]

In the formula (I), Ar¹ and Ar² each independently represent a directbond, an aromatic hydrocarbon group optionally having a substituent, oran aromatic heterocyclic group optionally having a substituent; Ar³ toAr⁵ each independently represent an aromatic hydrocarbon groupoptionally having a substituent, or an aromatic heterocyclic groupoptionally having a substituent. Ar¹ to Ar⁴ are divalent groups, and Ar⁵is a monovalent group.

The aromatic hydrocarbon group optionally having a substituent includes,for example, those derived from 6-membered monocyclic rings or di- topenta-condensed rings such as benzene ring, naphthalene ring, anthracenering, phenanthrene ring, perylene ring, tetracene ring, pyrene ring,benzopyrene ring, chrysene ring, triphenylene ring, acenaphthene ring,fluoranthene ring, fluorene ring.

The aromatic heterocyclic group optionally having a substituentincludes, for example, those derived from 5- or 6-membered monocyclicrings or di- to tetra-condensed rings such as furan ring, benzofuranring, thiophene ring, benzothiophene ring, pyrrole ring, pyrazole ring,imidazole ring, oxadiazole ring, indole ring, carbazole ring,pyrroloimidazole ring, pyrrolopyrazole ring, pyrrolopyrrole ring,thienopyrrole ring, thienothiophene ring, furopyrrole ring, furofuranring, thienofuran ring, benzisoxazole ring, benzisothiazole ring,benzimidazole ring, pyridine ring, pyrazine ring, pyridazine ring,pyrimidine ring, triazine ring, quinoline ring, isoquinoline ring,cinnoline ring, quinoxaline ring, phenanthridine ring, benzimidazolering, perimidine ring, quinazoline ring, quinazolinone ring, azurenering.

From the viewpoint of the solubility in organic solvent and the heatresistance, Ar¹ to Ar⁵ are preferably each independently a group derivedfrom a ring selected from a group consisting of benzene ring,naphthalene ring, anthracene ring, phenanthrene ring, triphenylene ring,pyrene ring, thiophene ring, pyridine ring and fluorene ring.

Ar¹ to Ar⁵ each are also preferably a divalent group composed of one ormore rings selected from the above-mentioned group and bonding to eachother either directly or via a group of —CH═CH—, more preferably abiphenylene ring or a terphenylene ring.

Not specifically defined, the substituent that the aromatic hydrocarbongroup and the aromatic heterocyclic group for Ar¹ to Ar⁵ may have apartfrom the crosslinking group to be mentioned below includes, for example,one or more selected from the following “group of substituents Z”.

[Group of Substituents Z]

Alkyl group having from 1 to 24 carbon atoms, preferably from 1 to 12carbon atoms, such as methyl group, ethyl group;

Alkenyl group having from 2 to 24 carbon atoms, preferably from 2 to 12carbon atoms, such as vinyl group;

Alkynyl group having from 2 to 24 carbon atoms, preferably from 2 to 12carbon atoms, such as ethynyl group;

Alkoxy group having from 1 to 24 carbon atoms, preferably from 1 to 12carbon atoms, such as methoxy group, ethoxy group;

Aryloxy group having from 4 to 36 carbon atoms, preferably from 5 to 24carbon atoms, such as phenoxy group, naphthoxy group, pyridyloxy group;

Alkoxycarbonyl group having from 2 to 24 carbon atoms, preferably from 2to 12 carbon atoms, such as methoxycarbonyl group, ethoxycarbonyl group;

Dialkylamino group having from 2 to 24 carbon atoms, preferably from 2to 12 carbon atoms, such as dimethylamino group, diethylamino group;

Diarylamino group having from 10 to 36 carbon atoms, preferably from 12to 24 carbon atoms, such as diphenylamino group, ditolylamino group,N-carbazolyl group;

Arylaminoalkyl group having from 6 to 36 carbon atoms, preferably from 7to 24 carbon atoms, such as phenylmethylamino group;

Acyl group having from 2 to 24 carbon atoms, preferably from 2 to 12carbon atoms, such as acetyl group, benzoyl group;

Halogen atom such as fluorine atom, chlorine atom;

Haloalkyl group having from 1 to 12 carbon atoms, preferably from 1 to 6carbon atoms, such as trifluoromethyl group;

Alkylthio group having from 1 to 24 carbon atoms, preferably from 1 to12 carbon atoms, such as methylthio group, ethylthio group;

Arylthio group having from 4 to 36 carbon atoms, preferably from 5 to 24carbon atoms, such as phenylthio group, naphthylthio group, pyridylthiogroup;

Silyl group having from 2 to 36 carbon atoms, preferably from 3 to 24carbon atoms, such as trimethylsilyl group, triphenylsilyl group;

Siloxy group having from 2 to 36 carbon atoms, preferably from 3 to 24carbon atoms, such as trimethylsiloxy group, triphenylsiloxy group;

Aromatic hydrocarbon group having from 6 to 36 carbon atoms, preferablyfrom 6 to 24 carbon atoms, such as phenyl group, naphthyl group;

Aromatic heterocyclic group having from 3 to 36 carbon atoms, preferablyfrom 4 to 24 carbon atoms, such as thienyl group, pyridyl group.

The above-mentioned substituents may further have a substituent, and itsexamples include those illustrated for the above-mentioned group ofsubstituents Z.

The molecular weight of the substituent that the aromatic hydrocarbongroup and the aromatic heterocyclic group for Ar¹ to Ar⁵ may have apartfrom the crosslinking group to be mentioned below is preferably at most500 inclusive of the group by which it is further substituted, morepreferably at most 250.

From the viewpoint that the solubility in organic solvent may furtherincrease, the substituent that the aromatic hydrocarbon group and thearomatic heterocyclic group for Ar¹ to Ar⁵ may optionally have arepreferably each independently an alkyl group having from 1 to 12 carbonatoms or an alkoxy group having from 1 to 12 carbon atoms.

In case where n is 2 or more, the repeating unit of the above formula(I) has at least two Ar⁴'s and Ar⁵'s. In this case, Ar⁴'s and Ar⁵'s eachmay be the same or different. Further, Ar⁴'s and Ar⁵'s each may bond toeach other either directly or via a linking group, thereby forming acyclic structure.

[1-3. Crosslinking Group]

T in the formula (I) is a group containing a crosslinking group. Inother words, the polymer compound (i) of the invention has a groupcontaining at least one crosslinking group in one molecule as thesubstituent. The crosslinking group means a group that reacts with thesame or a different group of other molecule existing around it, throughirradiation with heat and/or active energy rays, thereby forming a newchemical bond.

Above all, the crosslinking group is selected from the following <Groupof Crosslinking Groups T′> from the viewpoint of the easycrosslinkability thereof.

<Group of Crosslinking Groups T′>

(In the formulae, R²¹ to R²⁵ each independently represent a hydrogenatom or an alkyl group. Ar⁴¹ represents an aromatic hydrocarbon groupoptionally having a substituent, or an aromatic heterocyclic groupoptionally having a substituent.

The benzocyclobutene ring may have a substituent.

The substituents may together form a ring.)

The crosslinking group is preferably a cyclic ether group such as epoxygroup or oxetane group, or a cationic polymerizing group such as vinylether group, from the viewpoint of the high reactivity and the easycrosslinkability with organic solvent. Above all, especially preferredis an oxetane group from the viewpoint of easy controllability of thecationic polymerization speed; and also preferred is a vinyl ether groupthat hardly produces a hydroxyl group having a risk of degrading devicesin cationic polymerization.

As the crosslinking group, preferred is a group that brings aboutcyclization addition reaction, for example, an arylvinylcarbonyl groupsuch as cinnamoyl group, or a group derived from a benzocyclobutenering, from the viewpoint of further enhancing the electrochemicalstability.

In the molecule, the crosslinking group may direct bond to the aromatichydrocarbon group or the aromatic heterocyclic group in the molecule,but preferably bonds to the aromatic hydrocarbon group or the aromaticheterocyclic group via a divalent group composed of from 1 to 30 groupsselected from a group —O—, a group —C(═O)— and a group (optionallyhaving a substituent) —CH₂— and bonding to each other in any desiredorder. Specific examples of the crosslinking group bonding via thedivalent group, or that is, those of a group containing a crosslinkinggroup are as shown in the following <Group of crosslinkingGroup-Containing Groups T″>, to which, however, the invention should notbe limited.

<Group of Crosslinking Group-Containing Groups T″>

[1-4. Position of Crosslinking Group]

In the polymer compound (i) of the invention, Ar³ has a group Tcontaining a crosslinking group as the substituent.

In case where the polymer compound (i) of the invention has any othercrosslinking group than T, it may be in the repeating unit or may be inany other moiety than the repeating unit. However, R¹ and R² to bementioned below do not have a crosslinking group.

In case where a group containing a crosslinking group exists in anyother site than Ar³, the group is preferably in any of Ar¹, Ar², Ar⁴ andAr⁵ from the viewpoint that the crosslinking group is hardly degraded byreduction. However, when Ar¹, Ar² and Ar⁴ are fluorene groups, they donot have a group containing a crosslinking group as the substituent.This is because, when the polymer has a crosslinking group in theabove-mentioned position, the polymer may be more hardly degraded byreduction than in the fluorene ring.

For reducing the number of unreacted crosslinking groups, thecrosslinking groups are preferably only in T.

[1-5. Content Ratio of Crosslinking Groups]

The mean value of the number of the crosslinking groups that the polymercompound (i) of the invention has is preferably at least one in onemolecule, more preferably at least 2, also preferably at most 200, morepreferably at most 100.

The number of the crosslinking groups that the polymer compound (i) ofthe invention has may be expressed as the number thereof per themolecular weight of 1000.

When the number of the crosslinking groups that the polymer compound (i)of the invention has is expressed as the number per the molecular weightthereof of 1000, it is generally at most 3.0 per the molecular weight of1000, preferably at most 2.0, more preferably at most 1.0, and generallyat least 0.01, preferably at least 0.05.

When the number is larger than the upper limit, a flat film could not beobtained as it may be cracked, or the crosslinking density may increaseso that the unreacted crosslinking groups may increase in thecrosslinked layer and they may have some influence on the lifetime ofthe devices to be obtained. On the other hand, the number is smallerthan the lower limit, then the polymer may be insoluble in organicsolvent and could not form a multilayered laminate structure accordingto a wet film formation method.

The number or the crosslinking groups per the molecular weight of 1000in the polymer compound (i) of the invention may be computed from themolar ratio of the starting monomers in production and from thestructural formula of the polymer compound from which the terminal groupis removed.

For example, this is described with reference to the case of the productpolymer 3 produced in Production Example 35 given below.

In the product 35, the molecular weight of the repeating unit except theterminal group is 468.9 on average, and the number of the crosslinkinggroups therein is 0.2 per one repeating unit on average. The data arecomputed in simple proportion, and the number of the crosslinking groupsper the molecular weight of 1000 is 0.426.

[1-6. R¹ and R²]

R¹ and R² each independently represent a hydrogen atom, an aromatichydrocarbon group optionally having a substituent, an aromaticheterocyclic group optionally having a substituent, or an alkyl groupoptionally having a substituent, and R¹ and R² may bond to each other toform a ring.

The alkyl group optionally having a substituent is preferably a linearor branched alkyl group having from 1 to 8 carbon atoms, including, forexample, methyl group, ethyl group, n-propyl group, 2-propyl group,n-butyl group, isobutyl group, tert-butyl group, n-pentyl group, n-hexylgroup, n-octyl group, 2-ethylhexyl group, n-decyl group, n-dodecylgroup.

The aromatic hydrocarbon group optionally having a substituent, and thearomatic heterocyclic group optionally having a substituent includethose described in the above section, [1-2. Ar¹ to Ar⁵]. Preferredexamples are the same as therein.

In case where R¹ and R² each are an aromatic hydrocarbon group, anaromatic heterocyclic group or an alkyl group, the substituent that theymay have includes those described in the above section [Group orSubstituents Z]. Preferred examples are the same as therein.

In case where R¹ and R² bond to each other to form a ring, preferredexamples containing the fluorene ring are shown in the following<Specific Examples>, to which, however, the invention should not belimited.

Specific Examples

Above all, preferred are S-1, S-2, S-5 and S-9 from the viewpoint of theelectrochemical stability; more preferred is S-5 from the viewpoint ofthe heat stability; and even more preferred are S-1 and S-2 from theviewpoint of the high solubility in organic solvent before crosslinking.

[1-7. Regarding n]

In the formula (I), n indicates an integer of from 0 to 3.

Preferably, n is 0 from the viewpoint that the polymer compound may haveincreased solubility in organic solvent and may have increased filmformability. Also preferably, n is from 1 to 3 from the viewpoint thatthe polymer compound may have increased hole transport capability.

[1-8. Molecular Weight]

The weight-average molecular weigh (Mw) of the polymer compound (i) ofthe invention is generally at most 3,000,000, preferably at most1,000,000, more preferably at most 500,0000, and is generally at least1,000, preferably at least 2,500, even more preferably at least 5,000.

The number-average molecular weigh (Mn) of the polymer compound (i) ofthe invention is generally at least 3,000, preferably at least 6,000,and is generally at most 1,000,000, preferably at most 500,000. When theweight-average molecular weight or the number-average molecular weightis lower than the lower limit of the range, then the insolubility of thecrosslinked layer in organic solvent may lower and layer laminationwould be impossible, and the glass transition temperature may lower todetract from the heat resistance. When more than the upper limit of therange, then the polymer could not dissolve in organic solvent evenbefore crosslinking, and a flat film could not be formed.

The dispersity (Mw/Mn) of the polymer compound (i) of the invention isgenerally at most 3.5, preferably at most 2.5, more preferably at most2.0. When the dispersity of the polymer compound (i) is more than theupper limit of the range, then the polymer would be difficult to purifyand the solubility thereof in organic solvent may lower, and the chargetransfer capacity thereof may lower. The dispersity is ideally 1.0.

In general, the weight-average molecular weight is determined throughSEC (size exclusion chromatography). In SEC, a fragment having a highermolecular weight has a shorter elution time, and a fragment having alower molecular weight takes a longer elution time. Using a calibrationcurve computed from the elution time of polystyrene (standard sample)having a known molecular weight, the elution time of the sample to beanalyzed is converted into the molecular weight thereof, and theweight-average molecular weight of the sample is thus computed.

[1-9. Additional Repeating Unit]

Preferably, the polymer compound (i) of the invention contains arepeating unit represented by the following formula (I′), in which thenumber of the uncrosslinked groups may be reduced by controlling thenumber of the crosslinking groups therein whereby the drive lifetime ofthe devices to be obtained can be prolonged.

(In the formula, R¹¹ and R¹² each independently represent a hydrogenatom, an aromatic hydrocarbon group optionally having a substituent, anaromatic heterocyclic group optionally having a substituent, or an alkylgroup optionally having a substituent, R¹¹ and R¹² may bond to eachother to form a ring;

m indicates an integer of from 0 to 3;

Ar¹¹ and Ar¹² each independently represent a direct bond, an aromatichydrocarbon group optionally having a substituent, or an aromaticheterocyclic group optionally having a substituent;

Ar¹³ to Ar¹⁵ each independently represent an aromatic hydrocarbon groupoptionally having a substituent, or an aromatic heterocyclic groupoptionally having a substituent.

However, R¹¹ and R¹², and Ar¹¹ to Ar¹⁵ do not have a crosslinking groupas the substituent.)

(1-9-1. Ar¹¹ to Ar¹⁵)

Ar¹¹ and Ar¹² each independently represent a direct bond, an aromatichydrocarbon group optionally having a substituent, or an aromaticheterocyclic group optionally having a substituent; Ar¹³ to Ar¹⁵ eachindependently represent an aromatic hydrocarbon group optionally havinga substituent, or an aromatic heterocyclic group optionally having asubstituent. Ar¹¹, Ar¹² and Ar¹⁴ are divalent groups; and Ar¹³ and Ar¹⁵are monovalent groups.

Specific examples of the aromatic hydrocarbon group optionally having asubstituent and the aromatic heterocyclic group optionally having asubstituent for Ar¹¹ to Ar¹⁵ are the same as those described in theabove-mentioned section [1-2. Ar¹ to Ar⁵]. Preferred examples are thesame as therein. However, Ar¹¹ to Ar¹⁵ do not have a group containing acrosslinking group as the substituent.

(1-9-2. R¹¹ and R¹²)

R¹¹ and R¹² each independently represent a hydrogen atom, an aromatichydrocarbon group optionally having a substituent, an aromaticheterocyclic group optionally having a substituent, or an alkyl groupoptionally having a substituent.

Specific examples of the aromatic hydrocarbon group optionally having asubstituent, the aromatic heterocyclic group optionally having asubstituent, and the alkyl group optionally having a substituent for R¹¹and R¹² are the same as those described in the above-mentioned section[1-6. R¹ and R²]. Preferred examples are the same as therein.

(1-9-3. Regarding m)

m indicates an integer of from 0 to 3.

The above m is the same as n described in the section of [1-7. Regardingn]. Preferred examples are the same as therein.

[1-10. Ratio of Repeating Unit]

In case where the polymer compound (i) of the invention has a repeatingunit of the formula (I′), the ratio of the repeating unit of the formula(I′) to the repeating unit of the formula (I) [repeating unit of formula(I′)/repeating unit of formula (I)] is generally at least 0.01 molartimes, as the molar ratio of the starting monomers, preferably at least50 molar times, more preferably at least 80 molar times, and isgenerally at most 100 molar times, preferably at most 50 molar times.

The above range is preferred, within which the polymer compound isexcellent in the hole transport capability and the reduction resistance.Other advantages are that the drive voltage of the devices to beobtained could lower and the drive lifetime thereof may be long.

In case where the polymer compound (i) of the invention has any otherrepeating unit than the repeating unit of the formula (I) and therepeating unit of the formula (I′), the total content of the repeatingunit of the formula (I) and the repeating unit of the formula (I′) isgenerally at least 10 mol %, preferably at least 50 mol %, morepreferably at least 80 mol %.

The above range is preferred, within which the polymer compound isexcellent in the hole transport capability and the reduction resistance.Other advantages are that the drive voltage of the devices to beobtained could lower and the drive lifetime thereof may be long.

[1-11. Physical Properties]

The glass transition temperature of the polymer compound (i) of theinvention is generally not lower than 50° C., preferably not lower than80° C., more preferably not lower than 100° C., and is generally nothigher than 300° C.

The above range is preferred, within which the polymer compound isexcellent in the heat resistance and the drive lifetime of the devicesto be obtained may be long.

The ionization potential of the polymer compound (i) of the invention isgenerally at least 4.5 eV, preferably at least 4.8 eV, and is generallyat most 6.0 eV, preferably at most 5.7 eV.

The above range is preferred, within which the polymer compound isexcellent in the charge injection/transfer capability and the drivevoltage of the devices to be obtained could lower.

[1-12. Specific Examples]

Specific examples of the repeating unit of the formula (I) are shown inthe following <Group of Repeating Units of Formula (I), C>, to which,however, the invention should not be limited.

<Group of Repeating Units of Formula (I), C>

Specific examples of the repeating unit of the formula (I′) are shown inthe following <Group of Repeating Units of Formula (I′), D>, to which,however, the invention should not be limited.

<Group of Repeating Units of Formula (I′), D>

The other repeating unit than the repeating unit of the formula (I) andthe repeating unit of the formula (I′), which may be in the polymercompound (i) of the invention, may be any divalent group of therepeating unit mentioned below in which Ar^(a) and Ar^(c) do not containa triarylamine structure, as described in the section of <4. ProductionExample> given below.

Preferred examples of the other repeating units than the repeating unitof the formula (I) and the repeating unit of the formula (I′), which maybe in the polymer compound (i) of the invention, are shown in thefollowing <Group of Other Repeating Units E>, to which, however, theinvention should not be limited.

<Group of Other Repeating Units E>

<2. Polymer Compound (ii)>

The polymer compound (ii) of the invention is a polymer compoundcontaining a repeating unit of the following formula (II):

(In the formula, p indicates an integer of from 0 to 3;

Ar²¹ and Ar²² each independently represent a direct bond, an aromatichydrocarbon group optionally having a substituent, or an aromaticheterocyclic group optionally having a substituent;

Ar²³ to Ar²⁵ each independently represent an aromatic hydrocarbon groupoptionally having a substituent, or an aromatic heterocyclic groupoptionally having a substituent;

T² represents a group containing a group represented by the followingformula (IV).

However, Ar²¹ and Ar²² are not direct bonds at the same time.

Further, when Ar²¹, Ar²² and Ar²⁴ are fluorene rings, they do not have agroup containing a crosslinking group as the substituent.)

(The benzocyclobutene ring in the formula (IV) may have a substituent.The substituents may bond to each other to form a ring.)

[2-1. Structural Characteristics]

The structure of the group of the formula (IV) is especially stableafter crosslinked. Accordingly, when crosslinked, the solubility of thepolymer compound (ii) of the invention in organic solvent can be fullylowered.

Further, the compound has a group of the formula (IV) bonding to thearylamine moiety via at least one single bond therebetween. Therefore,it is favorable since the lone electron existing in the nitrogen atom ofthe arylamine moiety hardly flows to the group of the formula (IV) andsince the group of the formula (IV) is excellent in the electricstability. Another advantage is that the polymer compound hardlyaggregates and is therefore free from the problem of charge transportcapability depression of the polymer compound to be caused byaggregation thereof.

[2-2. Ar²¹ to Ar²⁵]]

Ar²¹ and Ar²² each independently represent a direct bond, an aromatichydrocarbon group optionally having a substituent, or an aromaticheterocyclic group optionally having a substituent;

Ar²³ to Ar²⁵ each independently represent an aromatic hydrocarbon groupoptionally having a substituent, or an aromatic heterocyclic groupoptionally having a substituent. Ar²³ and Ar²⁴ are divalent groups, andAr²⁵ is a monovalent group.

Specific examples of the aromatic hydrocarbon group optionally having asubstituent and the aromatic heterocyclic group optionally having asubstituent for Ar²¹ to Ar²⁵ are the same as those described in theabove-mentioned section [1-2. Ar¹ to Ar⁵]. The preferred examples arethe same as therein.

[2-3. Group of Formula (IV)]

T² in the formula (II) is a group that contains a group of the followingformula (IV). In other words, the polymer compound (ii) of the inventionhas at least one group containing a group of the following formula (IV)in one molecule:

(The benzocyclobutene ring in the formula (IV) may have a substituent.The substituents may bond to each other to form a ring.)

The substituent that the benzocyclobutene ring of the above formula (IV)may have includes those described in the above-mentioned section of[Group of Substituents Z]. Preferred examples are the same as therein;but most preferably, the ring is unsubstituted.

In the polymer compound (ii) of the invention, preferably, the group ofthe formula (IV) bonds to the aromatic hydrocarbon group or the aromaticheterocyclic group via a divalent group composed of from 1 to 30 groupsselected from a group —O—, a group —C(═O)— and a group (optionallyhaving a substituent) —CH₂— and bonding to each other in any desiredorder. Specifically, T² is preferably a group that contains a group ofthe formula (IV). This is because the benzocyclobutene ring of theformula (IV) is excellent in oxidation-reduction stability.

[2-4. Position of Group of Formula (IV)]

The polymer compound (ii) of the invention has a group that contains agroup of the formula (IV) as T².

The group T² that contains a group of the formula (IV) bonds to Ar²³;and therefore, as compared with a case where the group bonds to anyother position, the compound is favorable in that the formula isexcellent in oxidation-reduction stability and the compound hardlyaggregates.

In case where the polymer compound (ii) of the invention contain anyother group that contain a group of the formula (IV) than T², the groupmay be in the repeating unit or may be in any other site than therepeating unit.

In case where the group that contains a group of the formula (IV) is inany other side than Ar²³, the group is preferably in any of Ar²¹, Ar²²,Ar²⁴ or Ar²⁵ from the viewpoint that the group of the formula (IV) maybe hardly degraded by reduction. However, when Ar²¹, Ar²² and Ar²⁴ arefluorene rings, they do not have a group containing a crosslinking groupas the substituent.

[2-5. Content Ratio of Groups of Formula (IV)]

The content ratio of the groups of the formula (IV) in the polymercompound (ii) of the invention is the same as that in theabove-mentioned section [1-5. Content Ratio of Crosslinking Groups]where the crosslinking group is a group of the formula (IV). Preferredranges are the same as therein.

[2-6. Description of p]

In the formula (II), p indicates an integer of from 0 to 3.

The above p is the same as n described in the section of [1-7. Regardingn]. Preferred examples are the same as therein.

[2-7. Additional Repeating Units]

Preferably, the polymer compound (ii) of the invention further containsa repeating unit represented by the following formula (II′).

(In the formula (II′), q indicates an integer of from 0 to 3;

Ar³¹ and Ar³² each independently represent an aromatic hydrocarbon groupoptionally having a substituent, an aromatic heterocyclic groupoptionally having a substituent, or a double bond;

Ar³³, Ar³⁴ and Ar³⁵ each independently represent an aromatic hydrocarbongroup optionally having a substituent, or an aromatic heterocyclic groupoptionally having a substituent.

However, Ar³¹ and Ar³² are not direct bonds at the same time.

Ar³¹ to Ar³⁵ do not have a group containing a group of the formula (IV)as the substituent.

Further, when Ar³¹, Ar³² and Ar³⁴ are fluorene rings, they do not have agroup containing a crosslinking group as the substituent.)

(2-5-1. Ar³¹ to Ar³⁵)

Ar³¹ and Ar³² each independently represent an aromatic hydrocarbon groupoptionally having a substituent, an aromatic heterocyclic groupoptionally having a substituent, or a double bond;

Ar³³ to Ar³⁵ each independently represent an aromatic hydrocarbon groupoptionally having a substituent, or an aromatic heterocyclic groupoptionally having a substituent. Ar³¹, Ar³² and Ar³⁴ are divalentgroups; and Ar³³ and Ar³⁵ are monovalent groups.]

Specific examples of the aromatic hydrocarbon group optionally having asubstituent and the aromatic heterocyclic group optionally having asubstituent for Ar³¹ to Ar³⁵ are the same as those described in theabove section [1-2. Ar¹ to Ar⁵]. Preferred examples are the same astherein.

However, Ar³¹ to Ar³⁵ do not contain a group of the formula (IV) as thesubstituent.

Further, when Ar³¹, Ar³² and Ar³⁴ are fluorene rings, they do not have agroup containing a crosslinking group as the substituent.

(2-5-2. Regarding q)

In the formula (II′), q indicates an integer of from 0 to 3.

The above q is the same as n described in the section of [1.7. Regardingn]. Preferred examples are the same as therein.

[2-6. Ratio of Repeating Units]

In case where the polymer compound (ii) of the invention has a repeatingunit of the formula (II′), the ratio of the repeating units of theformula (II′) to the repeating units of the formula (II) [repeatingunits of formula (II′)/repeating units of formula (II)] is the same asthat described in the above section [1-10. Ratio of Repeating Unit]. Inother words, the repeating units of the formula (I) in the above sectionare replaced by the repeating units of the formula (II) in this case,and the repeating units of the formula (I′) therein are replaced by therepeating units of the formula (II′). Preferred examples are the same astherein. The polymer compound (ii) of the invention may contain anyother repeating unit than the repeating unit of the formula (II) and therepeating unit of the formula (II′).

[2-7. Physical Properties]

The physical properties of the polymer compound (ii) of the inventionare the same as those described in the above section [1-10. PhysicalProperties. Preferred examples are the same as therein.

[2-8. Specific Examples]

Preferred examples of the repeating unit of the formula (II) are shownin the following <Group of Repeating Units of Formula (II), F>, towhich, however, the invention should not be limited.

<Group of Repeating Units of Formula (II), F>

Of the specific examples described in the above section <Group ofRepeating Units of Formula (I), C>, the repeating units having a groupof the formula (IV) are also preferred examples of the repeating unit ofthe formula (II).

Preferred examples of the repeating unit of the formula (II′) are shownin the following <Group of Repeating Units of Formula (II′), G>, towhich, however, the invention should not be limited.

<Group of Repeating Units of Formula (II′), G>

Of the specific examples described in the above section <Group ofRepeating Units of Formula (I′) D>, those corresponding to the repeatingunit of the formula (II′) are also preferred examples of the repeatingunit of the formula (II′).

The other repeating unit than the repeating unit of the formula (II) andthe repeating unit of the formula (II′), which may be in the polymercompound (ii) of the invention, may be any divalent group of therepeating unit mentioned below in which Ar^(a) Ar^(c) do not contain atriarylamine structure, as described in the section <4. ProductionMethod> given below.

Preferred examples of the other repeating units than the repeating unitof the formula (II) and the repeating unit of the formula (II′), whichmay be in the polymer compound (ii) of the invention, are shown in thefollowing <Group of Other Repeating Units H>, to which, however, theinvention should not be limited.

<Group of Other Repeating Units H>

<3. Especially Preferred Polymer Compounds>

Especially preferably, the polymer compound of the invention is apolymer compound having at least one repeating unit selected from agroup of the following repeating units A, and at least one repeatingunit selected from a group of the following repeating units B.

<Group of Repeating Units A>

<Group of Repeating Units B>

<4. Production Method>

The polymer compound of the invention can be produced according to aknown method, using starting materials that are selected according tothe structure of the intended compound.

The polymer compound of the invention can be produced through sequentialpolymerization of a halide of a general formula (Va) with a secondaryamine of a general formula (Va) of with a boron compound of a generalformula (Vc) in the presence of a base such as potassium carbonate,sodium tert-butoxide or triethylamine, according to the formulamentioned below. If desired, a transition metal catalyst such as copperor palladium complex may be used.

In other words, the polymer compound of the invention can be producedthrough sequential polymerization of reacting the formula (Va) and theformula (Vb) to form an N—Ar bond (for example, in a mode ofBuchwald-Hartwig coupling or Ullmann coupling), or reacting the formula(Va) and the formula (Vc) to form an Ar—Ar bond (for example, in a modeof Suzuki coupling).

(In the formulae, X represents a halogen atom, or a sulfonate estergroup such as CF₃SO₂O—; Ar represents an aromatic hydrocarbon groupoptionally having a substituent or an aromatic heterocyclic groupoptionally having a substituent;

R′ represents a hydroxyl group or an alkoxy group that may bonds to eachother to form a ring;

Ar^(a), Ar^(b) and Ar^(c) each independently represent a divalentaromatic hydrocarbon group optionally having a substituent or a divalentaromatic heterocyclic group optionally having a substituent.)

However, in case where the polymer compound (i) of the invention isproduced, at least one of Ar^(a) or Ar^(b), as well as Ar^(a) or Ar^(c)contains a divalent group of the following formula (VI):

(In the formula, R⁵¹ and R⁵² each independently represent a hydrogenatom, an aromatic hydrocarbon group optionally having a substituent, anaromatic heterocyclic group optionally having a substituent, or an alkylgroup optionally having a substituent; and R⁵¹ and R⁵² may bond to eachother to form a ring.)

R⁵¹ and R⁵² are the same as R¹ and R² in the above-mentioned section[1-6. R¹ and R²]. Preferred examples are the same as therein.

Ar^(a) and Ar^(c) each independently represent an aromatic hydrocarbongroup optionally having a substituent or an aromatic heterocyclic groupoptionally having a substituent. In the above-mentioned productionmethod, preferred examples of Ar^(a) and Ar^(c) include those in <Groupof Divalent Groups optionally having substituent, A>, <Group of DivalentGroups optionally having substituent, B> and <Group of Divalent Groupsoptionally having substituent, C> to be mentioned below.

Preferred examples of Ar^(b) are represented by the formula (Vb),concretely including those in <Group of Specific Examples D> and <Groupof Specific Examples E> to be mentioned below.

The polymer compound of the invention can be produced by suitablyselected Ar^(a), Ar^(c) and the formula (Vb).

For example, in case where the polymer compound (i) of the invention isproduced, Ar^(a), Ar^(c) and the formula (Vb) are suitably so selectedthat the produced polymer compound could contain a divalent group of theformula (VI) and a group containing a crosslinking group, thereby givingthe polymer compound (i) of the invention.

The wording that at least one of Ar^(a) and Ar^(c) has a divalent groupof the formula (VI) means that, for example, Ar^(a) or Ar^(c) is a groupselected from <Group of Divalent Groups optionally having substituent,A> to be mentioned below.

Similarly, the wording that at least one of Ar^(a) and Ar^(c) has acrosslinking group means that, for example, Ar^(a) or Ar^(c) is a groupselected from <Group of Divalent Groups optionally having substituent,B> to be mentioned below.

Accordingly, Ar^(a) is selected from <Group of Divalent Groupsoptionally having substituent, A> and Ar^(c) is selected from <Group ofDivalent Groups optionally having substituent, B>, thereby giving thepolymer compound (i) of the invention.

The same shall apply to Ar^(a) and the formula (Vb).

In case where the polymer compound (ii) of the invention is produced,Ar^(a), Ar^(c) and the formula (Vb) are suitably so selected that theproduced polymer compound could contain a group of the formula (IV),thereby giving the polymer compound (ii) of the invention.

The wording that at least one of Ar^(a) and Ar^(c) has a group of theformula (IV) means that, for example, Ar^(a) or Ar^(c) is a group havinga group of the formula (IV) in the specific examples described in <Groupof Divalent Groups optionally having a substituent, B> to be mentionedbelow.

The same shall apply to Ar^(a) and the formula (Vb).

Preferred examples of the case where Ar^(a) and Ar^(c) each contain adivalent group of the formula (VI) but does not have a group containinga crosslinking group are shown in <Group of Divalent Groups optionallyhaving substituent, A> to be given below, to which, however, theinvention should not be limited.

<Group of Divalent Groups Optionally Having Substituent, A>

Preferred examples of the case where Ar^(a) and Ar^(c) do not have adivalent group of the formula (VI) but have a group containing acrosslinking group are shown in <Group of Divalent Groups optionallyhaving substituent, B> to be given below, to which, however, theinvention should not be limited.

<Group of Divalent Groups Optionally Having Substituent, B>

Preferred examples of the case where Ar^(a) and Ar^(c) do not have adivalent group of the formula (VI) and do not have a group containing acrosslinking group are shown in <Group of Divalent Groups optionallyhaving substituent, C> to be given below, to which, however, theinvention should not be limited.

<Group of Divalent Groups Optionally Having Substituent, C>

Preferred examples of the formula (Vb) not having a divalent group ofthe formula (VI) but having a group containing a crosslinking group areshown in <Group of Specific Examples D> to be given below, to which,however, the invention should not be limited.

<Group of Specific Examples D>

Preferred examples of the formula (Vb) not having a divalent group ofthe formula (VI) and not having a group containing a crosslinking groupare shown in <Group of Specific Examples E> to be given below, to which,however, the invention should not be limited.

<Group of Specific Examples E>

For methods of purification of compounds, herein usable are knowntechniques such as typically the methods described in “Handbook forSeparation Purification Technology” (1993, by the Chemical Society ofJapan), “High-Level Separation of Minor Components and Hardly-PurifyingSubstances by Chemical Conversion Method” (1988, by IPC), or thosedescribed in the section of “Separation and Purification” in “Lecture ofExperimental Chemistry, 4th Ed., 1” (1990, by the Chemical Society ofJapan). Concretely mentioned are extraction (including suspensionwashing, boiling washing, ultrasonic washing, acid/base washing),adsorption, absorption, melting, crystallization (includingrecrystallization and reprecipitation from solvent), distillation(normal pressure distillation, reduced pressure distillation),vaporization, sublimation (normal pressure sublimation, reduced pressuresublimation), ion exchange, dialysis, filtration, ultrafiltration,reverse osmosis, pressure osmosis, zone dissolution, electrophoresis,centrifugation, floating separation, precipitating separation, magneticseparation, various modes of chromatography (classification byconfiguration: column, paper, thin layer, capillary; classification bymobile phase: gas, liquid, micelle, ultra-critical fluid; separationmechanism; adsorption, partitioning, ion exchange, molecular sieving,chelation, gel filtration, exclusion, affinity), etc.

For analytical methods for product identification and puritydetermination, herein employable as needed are gas chromatography (GS),high-performance liquid chromatography (HPLC), high-speed amino acidanalyzer (polymer compound), capillary electrophoresis (CE), sizeexclusion chromatography (SEC), gel permeation chromatography (GPC),cross fractionation chromatography (CFC), mass analysis (MS, LC/MS,GC/MS, MS/MS), nuclear magnetic resonance (NMR (1H-NMR, 13C-NMR)),Fourier Transform IR spectrometer (FT-IR), UV-visible-near IRspectrophotometer (UV-VIS-NIR), electronic spin resonator (ESR),transmission electronic microscope (TEM-EDX), electron probemicroanalyzer (EPMA), metal element analysis (ion chromatography,induction coupled plasma emission spectrometry (ICP-AES), atomicabsorption spectroscopy (AAS), X-ray fluorescence spectrometer (XRF),nonmetal elementary analysis, minor component analysis (ICP-MS, GF-AAS,GD-MS), etc.

<5. Use of Polymer Compound>

The polymer compound of the invention is favorably used as acharge-transporting material, and is especially favorably used as anorganic electroluminescence element material. In case where the compoundis used as an organic electroluminescence element material, it isfavorably used as a charge-transporting material in the hole injectionlayer and/or the hole transport layer in an organic electroluminescenceelement.

As facilitating simple production of organic electroluminescenceelements, the polymer compound of the invention is favorably used in anorganic layer to be formed according to a wet film formation method.

<6. Net-like Polymer Compound>

The polymer compound of the invention undergoes crosslinking reaction byheating and/or by irradiation with active energy such as light to give anet-like polymer compound, as described in the following section <7.Composition for Organic Electroluminescence element> [Film FormationMethod]. The layer that contains the net-like polymer compound ispreferably a hole injection layer and/or a hole transport layer to bedescribed in detail hereinunder.

The degree of crosslinking of the network-structure polymer compound ofthe invention is generally at least 70%, preferably at least 80% and isgenerally at most 120%, preferably at most 110%, as measured accordingto the method described in the section “6-1. Method for Determination ofDegree of Crosslinking” mentioned below. Within the range, the layercontaining the net-like polymer compound does not mix with the layer tobe formed over that layer according to a wet film formation method, andis therefore favorable as not having any influence on the properties ofthe devices to be obtained.

[6-1. Method for Determination of Degree of Crosslinking]

In the invention, the degree of crosslinking is represented by L2/L1,for which the film thickness L1 and L2 are measured according to themethods mentioned below.

[6-1-1. Method of Film Formation, and Method of Measurement of FilmThickness L1]

A glass substrate having a size of 25 mm×37.5 mm is washed withultra-pure water, then dried with dry nitrogen, and washed withUV/ozone.

The sample to be analyzed (in general, this is a solution of the subjectcompound prepared so that the solid concentration of the compoundtherein could be 1% by weight) is applied onto the glass substrate in amode of spin coating to form a film thereon.

The spin coating condition is as follows:

[Spin Coating Condition]

Temperature: 23° C.

Relative humidity: 60%

Number of spinner rotations: 1500 rpm

Time of spinner rotation: 30 seconds

After thus coated, this is heated at 80° C. for 1 minute, and then driedunder heat at 230° C. for 60 minutes. The formed film is scraped out tohave a width of about 1 mm, and its thickness L1 (nm) is measured with athickness gauge (Tencor P-15, by KLA Tencor Corporation).

[6-1-2. Method of Measurement of Film Thickness L2]

After measurement of its thickness L1, the substrate is set on aspinner, and the same solvent as that used for the subject sample isdropwise given onto the site thereof at which its thickness wasmeasured, and after 10 seconds, this is spin-coated in the same manneras in the above-mentioned <spin coating condition>. Subsequently, thethickness of the film at the same site is measured, L2 (nm). The degreeof crosslinking is computed as L2/L1.

<7. Composition of Organic Electroluminescence Element>

The composition for organic electroluminescence element of the inventioncontains at least one polymer compound of the invention.

The composition for organic electroluminescence element of the inventionis for an organic electroluminescence element having an organic layerdisposed between an anode and a cathode; and in the device, in general,the composition is used as a coating liquid for forming the organiclayer according to a wet film formation method. Preferably, thecomposition for organic electroluminescence element of the invention isused for forming a hole transport layer of the organic layer.

In this, in case where one layer is present between the anode and thelight emission layer in an organic electroluminescent layer, this layeris referred to as “hole transport layer”; and in case where two or morelayers are present between them, then the layer adjacent to the anode isreferred to as “hole injection layer”, and the other layers aregenerically as “hole transport layer”. The layer between the anode andthe light emission layer may be generically referred to as “holeinjection/transport layer”.

The composition for organic electroluminescence element of the inventionis characterized by containing the polymer compound of the invention,and in general, it further contains a solvent.

The solvent is preferably one capable of dissolving the polymer compoundof the invention, and in general, it is a solvent capable of dissolvingthe polymer compound to a degree of at least 0.05% by weight at roomtemperature, preferably at least 0.5% by weight, more preferably atleast 1% by weight.

The composition for organic electroluminescence element of the inventionmay contain only one type or two or more types of the polymer compoundsof the invention.

The composition for organic electroluminescence element of the inventioncontains the polymer compound of the invention generally to a degree ofat least 0.01% by weight, preferably at least 0.05% by weight, morepreferably at least 0.1% by weight, and generally at most 50% by weight,preferably at most 20% by weight, more preferably at most 10% by weight.

The composition may contain various additives. In this case, the solventis preferably one capable of dissolving both the polymer compound of theinvention and the additives to a degree of at least 0.05% by weight,more preferably at least 0.5% by weight, even more preferably at least1% by weight.

The additive capable of promoting the crosslinking reaction of thepolymer compound of the invention, that may be in the composition forelectroluminescence element of the invention, includes a polymerizationinitiator such as alkylphenone compound, acylphosphine oxide compound,metallocene compound, oxime ester compound, azo compound, oniumcompound; and a light sensitizer such as condensed polycyclichydrocarbon, porphyrin compound, diaryl ketone compound. One or more ofthese may be used either singly or as combined.

In case where the composition for organic electroluminescence element ofthe invention is used for forming a hole injection layer, it preferablycontains an electron-receiving compound for lowering the resistancevalue of the formed layer.

The electron-receiving compound is preferably one having an oxidizingpower and having the ability of receiving an electron from theabove-mentioned hole-transporting compound. Concretely, preferred is acompound having an electron affinity of at least 4 eV, more preferablyat least 5 eV.

Examples of the electron-receiving compound include, for example,organic group-substituted onium salts such as4-isopropyl-4′-methyldiphenyliodonium tetrakis(pentafluorophenyl)borate;high-valent inorganic compounds such as iron(III) chloride (JP-A11-251067), ammonium peroxodisulfate; cyano compounds such astetracyanoethylene; aromatic boron compounds such astris(pentafluorophenyl)borane (JP-A 2003-31365); fullerene derivatives,iodine, etc.

Of the above compounds, preferred are organic group-substituted oniumsalts and high-valent inorganic compounds as having a strong oxidizingpower. Also preferred are organic group-substituted onium salts, cyanocompounds and aromatic boron compounds as having a high solubility invarious solvents and applicable to film formation according to a wetfilm formation method.

Specific examples of organic group-substituted onium salts, cyanocompounds and aromatic boron compounds that are suitable for use as theelectron-receiving compound are described in WO2005/089024, andpreferred examples described therein are applicable to the presentinvention. For example, compounds represented by the followingstructural formula may be mentioned, to which, however, the invention isnot limited.

One or more different types of electron-receiving compounds may be usedhere either singly or as randomly combined in any desired ratio.

The solvent to be in the composition for organic electroluminescenceelement of the invention is not specifically defined, but must dissolvethe polymer compound of the invention. Therefore, preferred are organicsolvents including aromatic compounds such as toluene, xylene,mesitylene, cyclohexylbenzene; halogen-containing solvents such as1,2-dichloroethane, chlorobenzene, o-dichlorobenzene; ether solventssuch as aliphatic ethers, e.g., ethylene glycol dimethyl ether, ethyleneglycol diethyl ether, propylene glycol 1-monomethyl ether acetate(PGMEA), aromatic ethers, e.g., 1,2-dimethoxybenzene,1,3-dimethoxybenzene, anisole, phenetol, 2-methoxytoluene,3-methoxytoluene, 4-methoxytoluene, 2,3-dimethylanisole,2,4-dimethylanisole; aliphatic esters such as ethyl acetate, n-butylacetate, ethyl lactate, n-butyl lactate; and ester solvents such asphenyl acetate, phenyl propionate, methyl benzoate, ethyl benzoate,isopropyl benzoate, propyl benzoate, n-butyl benzoate. One or more ofthese may be used here either singly or as combined.

The concentration of the solvent in the composition for organicelectroluminescence element of the invention is generally at least 10%by weight, preferably at least 50% by weight, more preferably at least80% by weight.

It is widely known that water may have the possibility of acceleratingthe performance degradation of organic electroluminescence element,especially the brightness depression thereof in continuous drive; andtherefore, for reducing the water content to remain in the coating film,those solvents having a solubility of water therein at 25° C. of at most1% by weight, preferably at most 0.1% by weight are preferred.

As the solvent to be in the composition for organic electroluminescenceelement of the invention, there is mentioned a solvent having a surfacetension at 20° C. of less than 40 dyn/cm, preferably at most 36 dyn/cm,more preferably at most 33 dyn/cm.

Specifically, in case where the crosslinking layer in the invention isformed according to a wet film formation method, its affinity to thebase is important. The uniformity of the coating film has greatinfluences on the uniformity and the stability of light emission byorganic electroluminescence element, and therefore, the coating liquidfor use in the wet film formation method is required to have a lowsurface tension in order that a uniform coating film having a higherleveling degree can be formed. Using the solvent of the type, thecrosslinking layer in the invention can be formed uniformly.

Specific examples of the low-surface-tension solvent are theabove-mentioned aromatic solvents such as toluene, xylene, mesitylene,cyclohexylbenzene, ester solvents such as ethyl benzoate, ether solventssuch as anisole, as well as trifluoromethoxyanisole,pentafluoromethoxybenzene, 3-(trifluoromethyl)anisole, ethyl(pentafluorobenzoate), etc.

The concentration of the solvent in the composition is generally atleast 10% by weight, preferably at least 30% by weight, more preferablyat least 50% by weight.

As the solvent to be in the composition for organic electroluminescenceelement of the invention, also mentioned is a solvent having a vaporpressure at 25° C. of at most 10 mmHg, preferably at most 5 mmHg, andgenerally at least 0.1 mmHg. Using the solvent of the type makes itpossible to produce a composition suitable for the process of producingan organic electroluminescence element according to a wet film formationmethod and suitable for the nature of the polymer compound of theinvention. Specific examples of the solvent of the type are theabove-mentioned aromatic solvents such as toluene, xylene mesitylene,ether solvents, and ester solvents. The concentration of the solvent inthe composition is generally at least 10% by weight, preferably at least30% by weight, more preferably at least 50% by weight.

As the solvent to be in the composition for organic electroluminescenceelement of the invention, also mentioned is a mixed solvent thatcomprises a solvent having a vapor pressure at 25° C. of at least 2mmHg, preferably at least 3 mmHg, more preferably at least 4 mmHg (itsupper limit is preferably at most 10 mmHg), and a solvent having a vaporpressure at 25° C. of less than 2 mmHg, preferably at most 1 mmHg, morepreferably at most 0.5 mmHg. Using the mixed solvent of the type makesit possible to form a homogeneous layer of the polymer compound of theinvention optionally containing an electron-receiving compound,according to a wet film formation method. The concentration of the mixedsolvent in the composition is generally at least 10% by weight,preferably at least 30% by weight, more preferably at least 50% byweight.

An organic electroluminescence element is produced by laminating anumber of layers of an organic compound, in which, therefore, theuniformity of the film thickness of the constitutive layers is extremelyimportant. In case where the layers are formed according to a wet filmformation method, various film formation methods are employable, forexample, a coating method of a spin coating method, a spray coatingmethod or the like, or a printing method of an inkjet method, a screenmethod or the like, depending on the nature of the film material and thebase. For example, a spraying method is effective for uniform filmformation on an intended surface, and is therefore favorable in a casewhere a layer of an organic compound is formed on an indented surfacehaving thereon patterned electrodes or pixels-partitioning walls. Incoating according to a spraying method, the liquid droplets as jettedfrom a nozzle toward the surface to be coated are as small as possiblefor attaining uniform film quality. For this, preferably, a solventhaving a high vapor pressure is mixed in the coating liquid so that apart of the solvent could evaporate away from the liquid droplets jettedout in the coating atmosphere and that fine liquid droplets could beformed just before the coating liquid reaches the substrate. Forobtaining more uniform film quality, a period of time must be securedfor leveling the liquid film formed on the substrate just after coating,and for attaining this object, there is employed a method of making thecoating liquid contain a suitable amount of a solvent capable ofevaporating away slowly, or that is, a solvent having a low vaporpressure.

Specific examples of the solvent having a vapor pressure at 25° C. offrom 2 mmHg to 10 mmHg are organic solvents such as xylene, anisole,cyclohexanone, toluene. The solvent having a vapor pressure at 25° C. oflower than 2 mmHg includes ethyl benzoate, methyl benzoate, tetralin,phenetol.

Regarding the blend ratio of the mixed solvent, the solvent having avapor pressure at 25° C. of not lower than 2 mmHg is in a ratio of atleast 5% by weight of the total amount of the mixed solvent, preferablyat least 25% by weight but less than 50% by weight, and the solventhaving a vapor pressure at 25° C. of lower than 2 mmHg is in a ratio ofat least 30% by weight of the total amount of the mixed solvent,preferably at least 50% by weight, more preferably at least 75% byweight but less than 95% by weight.

An organic electroluminescence element is produced by laminating anumber of layers of an organic compound, in which, therefore, theuniformity of the constitutive layers is needed. In case where thelayers are formed according to a wet film formation method, water maymix in the solution (composition) for film formation and water may mixin the coating film to detract from the uniformity of the film; andtherefore, the water content of the solution is preferably as small aspossible. Concretely, the water content of the composition forelectroluminescence element is preferably at most 1% by weight, morepreferably at most 0.1% by weight, even more preferably at most 0.05% byweight.

Materials that may be greatly degraded by water, such as cathode, aremuch used in an organic electroluminescence element, and therefore, fromthe viewpoint of preventing the degradation of the device, the existenceof water is unfavorable. As a method for reducing the water content inthe solution, for example, there are mentioned various techniques ofnitrogen gas sealing, use of drying agent, previous dehydration ofsolvent, use of solvent having a low solubility of water therein, etc.Above all, in case where a solvent having a low solubility of watertherein is used, it can prevent the phenomenon of whitening of thecoating film to be caused by water absorption by the film, and thesolvent of the type is favorable.

From this viewpoint, the composition for organic electroluminescenceelement of the invention preferably contains a solvent having asolubility of water therein at 25° C. of, for example, at most 1% byweight (preferably at most 0.1% by weight), in an amount of at least 10%by weight. The amount of the solvent satisfying the above-mentionedsolubility condition is more preferably at least 30% by weight, evenmore preferably at least 50% by weight.

Apart from the above-mentioned solvent, the composition for organicelectroluminescence element of the invention may contain any othersolvent, if desired. The additional solvent includes, for example,amides such as N,N-dimethylformamide, N,N-dimethylacetamide; anddimethyl sulfoxide.

The composition for organic electroluminescence element of the inventionmay contain various additives, for example, coating improver, such asleveling agent, defoaming agent.

[Film Formation Method]

As described in the above, an organic electroluminescence element isproduced by laminating a number of layers of an organic compound, andthe uniformity of the film quality is extremely important. In case wherethe layers are formed according to a wet film formation method, variousfilm formation methods are employable, for example, a coating method ofa spin coating method, a spray coating method or the like, or a printingmethod of an inkjet method, a screen method or the like, depending onthe nature of the film material and the base.

In the wet film formation method, the polymer compound of the inventionand other optional components (electron-receiving compound, crosslinkingreaction-accelerating additive, coating improver, etc.) are dissolved ina suitable solvent to prepare a composition for organicelectroluminescence element. The composition is applied onto anunderlayer on which the intended film is formed, according to a methodof spin coating method, a dip coating method or the like, then driedthereon, and crosslinked to thereby form a crosslinked layer in theinvention.

When the polymer compound of the invention is crosslinked to give anet-like polymer compound, it is generally heated.

The heating method is not specifically defined. For example, hot dryingis employed. Regarding the condition of hot drying, the layer formed ofthe composition for organic electroluminescence element of the inventionis heated generally at 120° C. or higher, preferably at 400° C. orhigher.

The heating time may be generally at least 1 minute, preferably at most24 hours. The heating means is not specifically defined. For example, amethod of heating the laminate having the formed layer on a hot plate orin an even may be employed. For example, the laminate may be heated on ahot plate at 120° C. or higher for at least 1 minute.

The heating method is not specifically defined. In heating and drying,the layer formed of the composition for organic electroluminescentcomposition is heated generally at a temperature not lower than 100° C.,preferably not lower than 120° C., more preferably not lower than 150°C., and generally not higher than 400° C., preferably not higher than350° C., more preferably not higher than 300° C. The heating time isgenerally at least 1 minute and is preferably at most 24 hours. Theheating means is not specifically defined. Employed is a method ofheating the laminate having a formed layer on a hot plate or in an oven.For example, the laminate may be heated on a hot plate at 120° C. orhigher for at least 1 minute.

For irradiation with active energy such as light, employed is a methodof irradiating the laminate directly with a UV-visible-IR light sourcesuch as ultra-high-pressure mercury lamp, high-pressure mercury lamp,halogen lamp, IR lamp, or a method of using a mask aligner or aconveyor-type illuminator with the above-mentioned light source builttherein, for the intended irradiation. For irradiation with activeenergy except light, for example, employed is a method of using anapparatus of radiating microwaves by the use of an magnetron, such as amicrowave oven.

The irradiation time is preferably one necessary for sufficientcrosslinking reaction, and in general, the irradiation may be for atleast 0.1 seconds but preferably for at most 10 hours.

The heating and the active energy irradiation with light or the like maybe effected either singly or as combined. When combined, the order ofthe operation is not specifically defined.

Preferably, the heating and the active energy irradiation with light orthe like is carried out in a waterless atmosphere such as a nitrogenatmosphere, for the purpose of reducing the water content in the treatedlayer and/or the amount of water adsorbed by the surface of the layer.For the same purpose, when the heating and/or the active energyirradiation with light or the like are combined, preferably, at leastthe step just before the formation of the light emission layer iscarried out in a waterless atmosphere such as a nitrogen gas atmosphere.

<8. Organic Electroluminescence Element>

The organic electroluminescence element of the invention has, on asubstrate, an anode, a cathode and an organic layer between the anodeand the cathode, wherein the organic layer has a layer containing thenet-like polymer compound of the invention (this may be referred to as acrosslinked layer).

In the organic electroluminescence element of the invention, thecrosslinked layer is preferably a hole injection layer and/or a holetransport layer.

Preferably, the crosslinked layer is formed of the composition forelectroluminescence element of the invention according to a wet filmformation method.

Preferably, the device has a light emission layer formed according to awet film formation method on the cathode side of the hole transportlayer. Also preferably, the device has a hole injection layer formedaccording to a wet film formation method on the anode side of the holetransport layer. Specifically, in the organic electroluminescenceelement of the invention, all the hole injection layer, the holetransport layer and the light emission layer are formed according to awet film formation method. Especially preferably, the light emissionlayer formed according to a wet film formation method is a layer of alow-molecular material.

FIG. 1 is a cross-sectional view graphically showing one example of thestructure of the organic electroluminescence element of the invention.The organic electroluminescence element shown in FIG. 1 comprises ananode, a hole injection layer, a hole transport layer, a light emissionlayer, a hole inhibition layer, an electron injection layer and acathode, as laminated on a substrate in that order. In thisconstitution, in general, the hole transport layer corresponds to theabove-mentioned, organic compound-containing layer of the invention.

[1] Substrate:

The substrate is a support for the organic electroluminescence element,for which is used a sheet of quartz or glass, a metal plate, a metalfoil, or a plastic film or sheet. Especially preferred are glass sheets,and transparent synthetic resin sheets of polyester, polymethacrylate,polycarbonate, polysulfone, etc. In case where a synthetic resin sheetis used, attention should be paid to the gas barrier property thereof.When the gas barrier capability of the substrate is too low, then it isunfavorable since the organic electroluminescence element may bedegraded by the outside air having passed through the substrate.Accordingly, preferably employed is a method of forming a dense siliconoxide film or the like on at least one surface of the synthetic resinsubstrate to secure the gas barrier property of the substrate.

[2] Anode:

The anode plays a role of hole injection into the layer on the side ofthe light emission layer to be mentioned below (hole injection layer orlight emission layer). The anode is generally formed of a metal such asaluminium, gold, silver, nickel, palladium, platinum; a metal oxide suchas indium and/or tin oxide; a metal halide such as copper iodide; carbonblack; or a conductive polymer such as poly(3-methylthiophene),polypyrrole, polyaniline. The anode is formed generally according to asputtering method or a vacuum evaporation method in many cases. Metalfine particles of silver or the like, fine particles of copper iodide orthe like, carbon black, conductive metal oxide fine particles, orconductive polymer fine powder may be dispersed in a suitable bindersolution, and the resulting dispersion may be applied onto a substrateto form an anode thereon. Further, a thin film of a conductive polymermay be formed on a substrate directly through electrolyticpolymerization, or a conductive polymer may be applied onto a substrateand dried thereon to form an anode (see Applied Physics Letters, 1992,Vol. 60, p. 2711). The anode may be formed of a laminate of multiplelayers of different substances.

The thickness of the anode differs depending on the necessarytransparency. In case where the anode is required to be transparent, itsvisible light transmittance is preferably at least 60%, more preferablyat least 80%, and in this case, the anode thickness is generally atleast 5 nm, preferably at least 10 nm, and is generally at most 1000 nm,preferably at most 500 nm. In case where the anode may benontransparent, the anode may be the same as the substrate. A differentconductive material may be further laminated on the anode.

For the purpose of removing the impurities from the anode and forcontrolling the ionization potential thereof to thereby enhance the holeinjection capability of the anode, the anode surface is preferablyprocessed with UV rays (UV)/ozone, or processed with oxygen plasma orargon plasma.

[3] Hole Injection Layer:

A hole injection layer is formed on the anode.

The hole injection layer is a layer for hole transportation to the layeron the side of the cathode from the anode.

In the organic electroluminescence element of the invention, the holeinjection layer may be omitted.

Preferably, the hole injection layer contains a hole-transportingcompound, more preferably a hole-transporting compound and anelectron-receiving compound. Further, the hole injection layerpreferably contains a cationic radical compound, more preferably acationic radical compound and a hole-transporting compound.

The hole injection layer may contain, if desired, a binder resin and acoating improver. Preferably, the binder resin hardly acts as a chargetrap.

The hole injection layer may be formed of an electron-receiving layeralone on the anode according to a wet film formation method; and acharge-transporting material composition may be directly applied thereonto form a layer laminated thereon. In this case, a part of thecharge-transporting material composition may interact with theelectron-receiving compound to form a layer excellent in holeinjectability.

(Hole-Transporting Compound)

The hole-transporting compound is preferably a compound having anionization potential of from 4.5 eV to 6.0 eV. However, when thecompound is used in a wet film formation method, the solubility of thecompound in the solvent for use in the wet film formation method ispreferably higher.

The hole-transporting compound is preferably the polymer compound of theinvention as excellent in film formability and having a high chargetransportation capability. In other words, the layer is preferablyformed of the composition for electroluminescence element of theinvention.

In case where any other compound than the polymer compound of theinvention is used as the hole-transporting compound, examples of thehole-transporting compound include aromatic amine compounds,phthalocyanine derivatives, porphyrin derivatives, oligothiophenederivatives, polythiophene derivatives. Of those, preferred are aromaticamine compounds from the viewpoint of the amorphous nature and thevisible transmittance thereof.

Not specifically defined in point of the type thereof, the aromaticamine compounds may be low-molecular compounds or polymer compounds; butfrom the viewpoint of the surface leveling effect thereof, preferred arepolymer compounds having a weight-average molecular weight of at least1000 and at most 1000000 (polymer-type hydrocarbon compounds withcontinuous repeating units).

As preferred examples of aromatic tertiary amine polymer compounds, alsomentioned are polymer compounds having a repeating unit of the followingformula (1):

(In the formula (1), Ar^(b1) and Ar^(b2) each independently represent anaromatic hydrocarbon group optionally having a substituent, or anaromatic heterocyclic group optionally having a substituent. Ar^(b3) toAr^(b5) each independently represent an aromatic hydrocarbon groupoptionally having a substituent, or an aromatic heterocyclic groupoptionally having a substituent. Z^(b) represents a linking groupselected from the following group of linking groups. Two groups ofAr^(b1) to Ar^(b5) bonding to the same N atom may bond to each other toform a ring.)

(In the above formulae, Ar^(b6) to Ar^(b16) each independently representa monovalent or divalent group derived from an aromatic hydrocarbon ringoptionally having a substituent or an aromatic hetero ring optionallyhaving a substituent. R^(b5) and R^(b6) each independently represent ahydrogen atom or a substituent.

To Ar^(b1) to Ar^(b16), applicable is a monovalent or divalent groupderived from an aromatic hydrocarbon ring or an aromatic hetero ring.These groups may be the same or different from each other. These groupmay have an additional substituent.

As specific examples of the aromatic tertiary amine polymer compoundhaving a repeating unit of the general formula (1), there are mentionedcompounds described in WO2005/089024.

The hole-transporting compound used as a material for the hole injectionlayer may contain any one of those compounds, or may contain two or moreof them.

In case where the layer contains two or more different types ofhole-transporting compounds, they may be combined in any desired manner.Preferably, one or more aromatic tertiary amine polymer compounds arecombined with one or more other hole-transporting compounds.

(Electron-Receiving Compound)

The electron-receiving compounds may be the same as those described inthe above-mentioned section <7. Composition for OrganicElectroluminescence element>. Preferred examples are the same astherein.

(Cationic Radical Compound)

The cationic radical compound is anionic compound composed of a cationicradical of a chemical species derived from a hole-transporting compoundby removing one electron therefrom, and a counter anion. However, incase where the cationic radical is derived from a hole-transportingpolymer compound, it has a structure derived from the polymer compoundby removing one electron from the repeating unit thereof.

Preferably, the cationic radical is a chemical species derived from theabove-mentioned hole-transporting compound by removing one electrontherefrom. More preferably, it is a chemical species derived from apreferred compound of those hole-transporting compounds by removing oneelectron therefrom, in view of the amorphous nature, the visibletransmittance, the heat resistance and the solubility thereof.

The cationic radical compound may be produced by mixing theabove-mentioned hole-transporting compound and the electron-receivingcompound. Specifically, when the hole-transporting compound is mixedwith the electron-receiving compound, then electron transfer occurs fromthe hole-transporting compound to the electron-receiving compound,thereby giving a cationic compound composed of the cationic radical ofthe hole-transporting compound and the counter anion.

Cationic radical compounds derived from polymer compounds such asPEDOT/PSS (Adv. Mater., 2000, Vol. 12, p. 481) or emeraldinehydrochloride (J. Phys. Chem., 1990, Vol. 94, 7716) can be producedthrough oxidative polymerization (dehydrogenation polymerization).

Oxidative polymerization as referred to herein comprises electrical orelectrochemical oxidation of a monomer in an acidic solution usingperoxodisulfate or the like. In the oxidative polymerization(dehydrogenation polymerization), the monomer is oxidized andpolymerized to give a cationic radical derived from the repeating unitof the polymer by removing one electron therefrom and having a counteranion derived from the acidic solution.

The hole injection layer may be formed according to a wet film formationmethod, or a dry film formation method such as vacuum evaporationmethod. Preferably, the layer is formed according to a wet filmformation method from the viewpoint of excellent film formability.

The thickness of the hole injection layer is generally at least 5 nm,preferably at least 10 nm, and is generally at most 1000 nm, preferablyat most 500 nm.

The content ratio of the electron-receiving compound relative to thehole-transporting compound in the hole injection layer is generally atleast 0.1 mol %, preferably at least 1 mol %, but is generally at most100 mol %, preferably at most 40 mol %.

(Other Constitutive Material)

Any other component than the above-mentioned hole-transporting compoundand the electron-receiving compound may be incorporated in the materialof the hole injection layer, not greatly detracting from the advantageof the invention. Examples of the additional components are variouslight-emitting materials, electron-transporting compounds, binderresins, coating improvers, etc. Either singly or as combined, one ormore such additional components may be incorporated in any desiredcombination and in any desired blend ratio.

(Solvent)

Preferably, at least one solvent in the composition for forming holeinjection layer according to a wet film formation method is a compoundcapable of dissolving the above-mentioned constitutive material for thehole injection layer. Preferably, the boiling point of the solvent isgenerally not lower than 110° C., more preferably not lower than 140°C., even more preferably not lower than 200° C., and is generally nothigher than 400° C., more preferably not higher than 300° C. When theboiling point of the solvent is too low, the drying speed may be toohigh and the film quality may worsen. When the boiling point of thesolvent is too high, then the temperature in the drying step must behigh and such a high temperature may have some negative influence on theother layers and the substrate.

The solvent includes, for example, ether solvents, ester solvents,aromatic hydrocarbon solvents, amide solvents.

The ether solvents include, for example, aliphatic ethers such asethylene glycol dimethyl ether, ethylene glycol diethyl ether, propyleneglycol 1-monomethyl ether acetate (PGMEA); aromatic ethers such as1,2-dimethoxybenzene, 1,3-dimethoxybenzene, anisole, phenetol,2-methoxytoluene, 3-methoxytoluene, 4-methoxytoluene,2,3-dimethylanisole, 2,4-dimethylanisole.

The ester solvents include, for example, aromatic esters such as phenylacetate, phenyl propionate, methyl benzoate, ethyl benzoate, propylbenzoate, n-butyl benzoate.

The aromatic hydrocarbon solvents include, for example, toluene, xylene,cyclohexylbenzene, 3-isopropylbiphenyl, 1,2,3,4-tetramethylbenzene,1,4-diisopropylbenzene, cyclohexylbenzene, methylnaphthalene.

The amide solvents include, for example, N,N-dimethylformamide,N,N-dimethylacetamide.

In addition, dimethyl sulfoxide is also usable.

Either singly or as combined, one or more such solvents are usable inany desired combination and in any desired blend ratio.

(Film Formation Method)

After the composition for forming hole injection layer is prepared, thecomposition is applied onto an underlying layer on which the holeinjection layer is to be formed (generally anode), and then dried toform the intended hole injection layer thereon.

The temperature in the film forming step is preferably not lower than10° C., more preferably not lower than 50° C. for the purpose ofpreventing the film from being cracked owing to crystal formation in thecomposition.

The relative humidity in the film forming step is not specificallydefined so far as it does not greatly detract from the advantage of theinvention, but is generally at least 0.01 ppm and is generally at most80%.

After the coating, the film of the composition for hole injection layeris heated generally by heating or the like. For drying the film,generally employed is a heating step. Examples of the heating means foruse in the heating step include a clean oven, a hot plate, an IR ray, ahalogen heater, microwave irradiation. Above all, preferred are a cleanoven and a hot plate for homogeneously heating the entire film.

The heating temperature in the heating step is preferably not lower thanthe boiling point of the solvent used in the hole injectionlayer-forming composition so far as it does not greatly detract from theadvantage of the invention. In case where a mixed solvent of two or moredifferent types of solvents is used in the hole injection layer-formingcomposition, preferably, the film of the composition is heated at atemperature not lower than the boiling point of at least one of themixed solvent. In consideration of the elevation of the boiling point ofthe solvent, the film is preferably heated at a temperature not lowerthan 120° C. and not higher than 410° C. in the heating step.

In the heating step, preferably, the heating temperature is not lowerthan the boiling point of the solvent in the hole injectionlayer-forming composition. The heating time is not specifically definedso far as the coating film is not fully crosslinked, but is preferablyat least 10 seconds and is generally at most 180 minutes. When theheating time is too long, the component of the other layer may diffuse;but when too short, the hole injection layer may be inhomogeneous. Theheating may be effected twice.

<Formation of Hole Injection Layer by Vacuum Evaporation Method>

In case where the hole injection layer is formed through vacuumevaporation, one or more of the constitutive materials for the holeinjection layer (the above-mentioned hole-transporting layer,electron-receiving layer, etc.) are put in a crucible set in a vacuumchamber (in case where two or more different types of materials areused, they are individually put in different crucibles), then the vacuumchamber is degassed with a vacuum pump to 10⁻⁴ Pa or so, and thereafterthe crucible is heated (in case where two or more different types ofmaterials are used, the respective crucibles are heated) whereby thematerial is evaporated under control of the evaporation rate (in casewhere two or more different types of materials are used, the evaporationrate of every material is individually controlled), and thus a holeinjection layer is thereby formed on the anode of the substrate arrangedto face the crucible. In case where two or more different types ofmaterials are used, their mixture may be put in one crucible and heatedand evaporated to form a hole injection layer.

The vacuum degree in vapor deposition is not specifically defined so faras it does not greatly detract from the advantage of the invention, butis generally at least 0.1×10⁻⁶ Torr (0.13×10⁻⁴ Pa) and at most 9.0×10⁻⁶Torr (12.0×10⁻⁴ Pa). The deposition speed is not also specificallydefined so far as it does not greatly detract from the advantage of theinvention, but is generally at least 0.1 angstrom/sec and at most 5.0angstrom/sec. The film formation temperature in vapor deposition is notspecifically defined so far as it does not greatly detract from theadvantage of the invention, but is preferably not lower than 10° C. andpreferably not higher than 50° C.

The thickness of the hole injection layer is generally at least 5 nm,preferably at least 10 nm, and is generally at most 1000 nm, preferablyat most 500 nm.

[4] Hole Transport Layer:

The hole transport layer may be formed on a hole injection layer, ifany, or may be formed on an anode in case where the device does not havea hole injection layer. The organic electroluminescence element of theinvention may have a constitution with no hole transport layer.

The material to form the hole transport layer is preferably one having ahigh hole transporting capability and capable of efficientlytransporting the injected hole. Accordingly, the material is preferablyone having a low ionization potential, having high transparency tovisible light, having a high hole mobility, excellent in stability, andhardly generating impurities to be traps during production and use. Inmany cases, the hole transport layer is adjacent to a light emissionlayer, and therefore it is desirable that the material does notextinguish the light from the light emission layer and does not form anexciplex with the light emission layer to cause efficiency depression.

From the above-mentioned viewpoint, the hole-transporting compound ispreferably the polymer compound of the invention. In case where anyother compound than the polymer compound of the invention is used as thehole-transporting compound, a constitutive material heretofore used forhole transport layer may be used here. For example, those exemplified inthe above for the hole-transporting compound for use in the holeinjection layer may be used. In addition, also usable are aromaticdiamines containing at least two tertiary amines and having at least twocondensed aromatic rings bonding to the nitrogen atom such as typically4,4′-bis[N-(1-naphthyl)-N-phenylamino]biphenyl (JP-A 5-234681), aromaticamine compounds having a starburst structure such as4,4′,4″-tris(1-naphthylphenylamino)triphenylamine (J. Lumin., Vols.72-74, p. 985, 1997), aromatic amine compounds of triphenylaminetetramer (Chem. Commun., p. 2175, 1996), spiro compounds such as2,2′,7,7′-tetrakis-(diphenylamino)-9,9′-spirofluorene (Synth. Metals,Vol. 91, p. 209, 1997), and carbazole derivatives such as4,4′-N,N′-dicarbazole-biphenyl. Further usable are, for example,polyvinylcarbazole, polyvinyltriphenylamine (JP-A 7-53953), polyaryleneether sulfones containing tetraphenylbenzidine (Polym. Adv. Tech., Vol.7, p. 33, 1996).

In case where the hole transport layer is formed according to a wet filmformation method, a hole transport layer-forming composition isprepared, then it is applied, and heated and dried, like that for theformation of the hole injection layer.

The hole transport layer-forming composition contains a solvent inaddition to the above-mentioned, hole-transporting compound. The solventto be used is the same as that used in the hole injection layer-formingcomposition. The coating condition and the heating and drying conditionare also the same as those in the formation of the hole injection layer.

In case where the hole transport layer is formed through vacuumevaporation, the condition for film formation is the same as that in theformation of hole injection layer.

Apart from the hole-transporting compound, the hole transport layer maycontain various light-emitting materials, electron-transportingcompounds, binder resins, coating improvers, etc.

The hole transport layer may be a layer formed by crosslinking acrosslinking compound. The crosslinking compound is a compound having acrosslinking group, and forms a net-like polymer compound bycrosslinking.

Examples of the crosslinking group are cyclic ether groups such asoxetane group, epoxy group; unsaturated double bond-having groups suchas vinyl group, trifluorovinyl group, styryl group, acrylic group,methacryloyl group, cinnamoyl group; benzocyclobutene ring-derivedgroups.

The crosslinking compound may be any of monomers, oligomers or polymers.One or more different types of crosslinking compounds may be used hereeither singly or as randomly combined in any desired ratio.

As the crosslinking compound, preferably used is a hole-transportingcompound having a crosslinking group. Examples of the hole-transportingcompound include nitrogen-containing aromatic compound derivatives suchas pyridine derivatives, pyrazine derivatives, pyrimidine derivatives,triazine derivatives, quinoline derivatives, phenanthroline derivatives,carbazole derivatives, phthalocyanine derivatives, porphyrinderivatives; triphenylamine derivatives; silole derivatives;oligothiophene derivatives, condensed polycyclic aromatic derivatives,metal complexes. Of those, preferred are nitrogen-containing aromaticderivatives such as pyridine derivatives, pyrazine derivatives,pyrimidine derivatives, triazine derivatives, quinoline derivatives,phenanthroline derivatives, carbazole derivatives; triphenylaminederivatives, silole derivatives, condensed polycyclic aromaticderivatives and metal complexes; and, in particular, more preferred aretriphenylamine derivatives.

In case where the hole transport layer is formed by crosslinking acrosslinking compound, in general, the crosslinking compound isdissolved or dispersed in a solvent to prepare a hole transportlayer-forming composition, and this is applied and crosslinked accordingto a wet film formation method.

In addition to the crosslinking compound, the hole transportlayer-forming composition may contain an additive for promotingcrosslinking reaction. Examples of the additive for promotingcrosslinking reaction include polymerization initiators andpolymerization promoters such as alkylphenone compounds, acylphosphineoxide compounds, metallocene compounds, oxime ester compounds, azocompounds, onium salts; photosensitizers such as condensed polycyclichydrocarbons, porphyrin compounds, diaryl ketone compounds.

In addition, the composition may further contain a coating improver suchas leveling agent, defoaming agent; an electron-receiving compound; abinder resin, etc.

The hole transport layer-forming composition contains a crosslinkingcompound generally in an amount of not smaller than 0.01% by weight,preferably not smaller than 0.05% by weight, more preferably not smallerthan 0.1% by weight, and generally in an amount of not larger than 50%by weight, preferably not larger than 20% by weight, more preferably notlarger than 10% by weight.

The hole transport layer-forming composition containing a crosslinkingcompound in such a concentration is applied onto the underlying layer(generally, hole injection layer), and then heated and/or irradiatedwith active energy such as light to thereby crosslink the crosslinkingcompound to give a net-like polymer compound.

The condition of temperature and humidity in coating, and the heatingcondition after coating are the same as those for the method describedin the above section <7. Organic Electroluminescence element>[FilmFormation Method]. Preferred embodiments are the same as therein.

The thickness of the hole transport layer is generally at least 5 nm,preferably at least 10 nm, and is generally at most 1000 nm, preferablyat most 500 nm.

[5] Light Emission Layer:

The light emission layer is formed on the hole transport layer, if any;and in case where the device does not have a hole transport layer buthas a hole injection layer, the light emission layer is formed on thehole injection layer; and in case where the device does not have a holetransport layer and a hole injection layer, the light emission layer isformed on the anode.

The light emission layer may be independent of the above-mentioned holeinjection layer and hole transport layer, and of a hole inhibitionlayer, an electron transport layer and others to be mentioned below.However, not forming an independent light emission layer, the otherorganic layers such as the hole transport layer and the electrontransport layer may serve additionally as the light emission layer.

The light emission layer is a layer to be the main light-emittingsource, which is, between the electrodes given an electric field,excited through recombination of the hole injected thereinto directlyfrom the anode or via the hole injection layer or the hole transportlayer, and the electron injected thereinto directly from the cathode orvia the cathode buffer layer, the electron transport layer or the holeinhibition layer.

The light emission layer may be formed in any desired method, notgreatly detracting from the advantage of the invention, but is formed onthe anode, for example, according to a wet film formation method of avacuum evaporation method. However, in case where a large-area lightemission device is produced, preferred is a wet film formation method.The wet film formation method and the vacuum evaporation method may beattained in the same manner as that for the formation of the holeinjection layer.

The light emission layer contains at least a material having alight-emitting nature (light-emitting material), and preferably containsa material having a nature of hole transportation (hole-transportingmaterial) or a material having a nature of electron transportation(electron-transporting material). Further, the light emission layer maycontain any other ingredients, not overstepping the spirit and the scopeof the invention. From the viewpoint of forming the light emission layeraccording to a wet film formation method as mentioned below, thesematerials are preferably low-molecular materials.

As the light-emitting material, usable is any known material. Forexample, it may be a fluorescent light-emitting material or aphosphorescent light-emitting material; however, from the viewpoint ofthe internal quantum efficiency, preferred is a phosphorescentlight-emitting material.

For the purpose of increasing the solubility in organic solvent, it isimportant to lower the symmetricity and the rigidity of the molecules ofthe light-emitting material and to introduce an oleophilic substituentsuch as alkyl group into the material.

Examples of fluorescent dyes of light-emitting materials are mentionedbelow; however, the fluorescent dyes for use herein are not limited tothe following examples.

Fluorescent light-emitting materials of giving blue light emission (bluefluorescent dyes) include, for example, naphthalene, chrysene, perylene,pyrene, anthracene, coumarin, p-bis(2-phenylethenyl)benzene and theirderivatives.

Fluorescent dyes of giving green light emission (green fluorescent dyes)include, for example, quinacridone derivatives, coumarin derivatives,aluminium complexes such as Al(C₉H₆NO)₃.

Fluorescent light-emitting materials of giving yellow light emission(yellow fluorescent dyes) include, for example, rubrene, perimidonederivatives.

Fluorescent light-emitting materials of giving red light emission (redfluorescent dyes) include, for example, DCM(4-(dicyanomethylene)-2-methyl-6-(p-dimethylaminostyryl)-4H-pyran)compounds, benzopyran derivatives, rhodamine derivatives,benzothioxanthene derivatives, azabenzothioxanthene.

Concretely, phosphorescent light-emitting materials includetris(2-phenylpyridine)iridium, tris(2-phenylpyridine)ruthenium,tris(2-phenylpyridine)palladium, bis(2-phenylpyridine)platinum,tris(2-phenylpyridine)osmium, tris(2-phenylpyridine)rhenium,octaethyl-platinum-porphyrin, octaphenyl-platinum-porphyrin,octaethyl-palladium-porphyrin, octaphenyl-palladium-porphyrin.

Polymer-type light-emitting materials include polyfluorene materialssuch as poly(9,9-dioctylfluorene-2,7-diyl),poly[(9,9-dioctylfluorene-2,7-diyl)-co-(4,4′-(N-(4-sec-butylphenyl))diphenylamine)],poly[(9,9-dioctylfluorene-2,7-diyl)-co-(1,4-benzo-2{2,1′-3}-triazole)];polyphenylenevinylene materials such aspoly[2-methoxy-5-(2-methylhexyloxy)-1,4-phenylenevinylene].

In addition, the polymer compound of the invention can be used as thelight-emitting material.

The molecular weight of the compound to be used as the light-emittingmaterial may be any desired one, not greatly detracting from theadvantage of the invention; but in general, it is at most 10000,preferably at most 5000, more preferably at most 4000, even morepreferably at most 3000, and is generally at least 100, preferably atleast 200, more preferably at least 300, even more preferably at least400. When the molecular weight of the light-emitting material is toosmall, then the heat resistance may be significantly low, or thematerial may be a cause of gas generation, or the material may lower thefilm quality in film formation, or the migration of the material maycause morphology change in the organic electroluminescence element. Onthe other hand, when the molecular weight of the light-emitting materialis too large, then the organic compound may be difficult to purify, orthe a lot of time may be taken in dissolving the material in solvent.

Any one or more of the above-mentioned light-emitting materials may beused here either singly or as randomly combined in any desired ratio.

The proportion of the light-emitting material in the light emissionlayer may be any desired one, not greatly detracting from the advantageof the invention, but is preferably at least 0.05% by weight and ispreferably at most 35% by weight. When the amount of the light-emittingmaterial is too small, then there may be a possibility of light emissionunevenness; but when too large, there may be a possibility of currentefficiency depression. In case where two or more different types oflight-emitting materials are used as combined, the total content thereofis controlled to fall within the above range.

Examples of low-molecular hole-transporting materials include thecompounds mentioned above as examples of the hole-transporting materialsfor the hole transport layer, as well as aromatic diamines containing atleast two tertiary amines and having at least two condensed aromaticrings substituted on the nitrogen atom, such as typically4,4′-bis[N-(1-naphthyl)-N-phenylamino]biphenyl (JP-A 5-234681), aromaticamine compounds having a starburst structure such as4,4′,4″-tris(1-naphthylphenylamino)triphenylamine (Journal ofLuminescence, 1977, Vols. 72-74, p. 985), aromatic amine compounds oftriphenylamine tetramer (Chemical Communications, 1996, p. 2175), spirocompounds such as 2,2′,7,7′-tetrakis-(diphenylamino)-9,9′-spirofluorene(Synthetic Metals, 1997, Vol. 91, p. 209).

Examples of low-molecular electron-transporting materials include2,5-bis(1-naphthyl)-1,3,4-oxadiazole (BND),2,5-bis(6′-(2′,2″-bipyridyl))-1,1-dimethyl-3,4-diphenylsilole(PyPySPyPy), bathophenanthroline (BPhen),2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline (BCP, bathocuproin),2-(4-biphenyl)-5-(p-tert-butylphenyl)-1,3,4-oxadiazole (tBu-PBD),4,4′-bis(9-carbazole)-biphenyl (CBP), 9,10-di-(2-naphthyl)anthracene(ADN).

Preferably, these hole-transporting material and electron-transportingmaterial serve as a host material in the light emission layer. Specificexamples of host materials usable herein are described in JP-A2007-067383, 2007-88433 and 2007-110093, and preferred examples thereofare also described therein.

For forming the light emission layer, employable are a wet filmformation method and a vacuum evaporation method. As described in theabove, a wet film formation method is preferred from the viewpoint thata homogeneous and defectless thin film is easy to produce, the time tobe taken for the film formation may be short, and further the method canenjoy the crosslinking effect of the hole transport layer brought aboutby the organic compound of the invention. In case where the lightemission layer is formed according to a wet film formation method, theabove-mentioned materials are dissolved in a suitable solvent to preparea coating solution, and this is applied on the above-mentioned, formedhole transport layer to form a film thereon, and dried to remove thesolvent. The forming method is the same as the forming method for thehole transport layer mentioned above.

The thickness of the light emission layer is generally at least 3 nm,preferably at least 5 nm and is generally at most 300 nm, preferably atmost 100 nm.

[6] Hole Inhibition Layer:

A hole inhibition layer 6 may be provided between the light emissionlayer 5 and the electron injection layer 8 to be mentioned below. Thehole inhibition layer 6 is a layer to be laminated on the light emissionlayer 5 so that it is adjacent to the interface of the light emissionlayer 5 on the side of the cathode 9.

The hole inhibition layer 6 plays a role of inhibiting the hole movingfrom the anode 2 from reaching the cathode 9, and a role of efficientlytransporting the electron injected from the cathode 9 toward the lightemission layer 5.

The physical properties necessary for the material constituting the holeinhibition layer 6 are that the electron mobility is high and the holemobility is low, the energy gap (difference between HOMO and LUMO) islarge and the excited triplet level (T1) is high. The material for thehole inhibition layer satisfying the requirements includes, for example,mixed ligand complexes such asbis(2-methyl-8-quinolato)(phenolato)aluminium,bis(2-methyl-8-quinolato)(triphenylsilanolato)aluminium; metal complexessuch asbis(2-methyl-8-quinolato)aluminium-μ-oxo-bis(2-methyl-8-quinolato)aluminiumbinuclear metal complex; styryl compounds such as distyrylbiphenylderivatives (JP-A 11-242996); triazole derivatives such as3-(4-biphenylyl)-4-phenyl-5(4-tert-butylphenyl)-1,2,4-triazole (JP-A7-41759); phenanthroline derivatives such as bathocuproin (JP-A10-79297). Further, compounds having at least one 2,4,6-substitutedpyridine ring as in WO2005/022962 are also preferred as the material forthe hole inhibition layer 6.

One or more different types of materials may be used for the holeinhibition layer 6, either singly or as randomly combined in any desiredratio.

The method of forming the hole inhibition layer 6 is not specificallydefined. Accordingly, the layer may be formed according to a wet filmformation method, a vapor deposition method or any other method.

The thickness of the hole inhibition layer 6 may be any desired one, notgreatly detracting from the advantage of the invention, but in generalit is at least 0.3 nm, preferably at least 0.5 nm and is generally atmost 100 nm, preferably at most 50 nm.

[7] Electron Transport Layer:

The electron transport layer is provided between the light emissionlayer and the electron injection layer for further enhancing the currentefficiency of the device.

The electron transport layer is formed of a compound capable ofefficiently transporting the electron injected from the cathode towardthe light emission layer, between the electrodes given an electricfield. The electron-transporting compound to be used for the electrontransport layer must be a compound having a high electron injectionefficiency from the cathode or the electron injection layer and having ahigh electron mobility and capable of efficiently transporting theinjected electron.

The material satisfying the requirements includes metal complexes suchas 8-hydroxyquinoline aluminium complex (JP-A 59-194393);10-hydroxybenzo[h]quinoline metal complexes, oxadiazole derivatives,distyrylbiphenyl derivatives, silole derivatives, 3- or 5-hydroxyflavonemetal complexes, benzoxazole metal complexes, benzothiazole metalcomplexes, trisbenzimidazolylbenzene (U.S. Pat. No. 5,645,978),quinoxaline compounds (JP-A 6-207169), phenanthroline derivatives (JP-A5-331459), 2-t-butyl-9,10-N,N′-dicyanoanthraquinonediimine, n-typehydrogenated amorphous silicon carbide, n-type zinc sulfide, n-type zincselenide.

The lower limit of the thickness of the electron transport layer isgenerally 1 nm, preferably 5 nm or so; and the upper limit thereof isgenerally 300 nm, preferably 100 nm or so.

The electron transport layer is laminated on the hole inhibition layeraccording to a wet film formation method or a vacuum evaporation methodin the same manner as above. In general, a vacuum evaporation method isemployed.

[8] Electro Injection Layer:

The electron injection layer plays a role of efficiently injecting theelectron injected from the cathode to the electron transport layer orthe light emission layer.

For efficient electron injection, the material for forming the electroninjection layer is preferably a metal having a low work function. Itexamples include alkali metals such as sodium, cesium; alkaline earthmetals such as barium, calcium. Its thickness is generally at least 0.1nm and is preferably at most 5 nm.

Further, doping an organic electron-transporting material such astypically a nitrogen-containing heterocyclic compound, e.g.,bathophenanthroline, or a metal complex, e.g., 8-hydroxyquinolinealuminium complex mentioned below, with an alkali metal such as sodium,potassium, cesium, lithium or rubidium (as described in JP-A 10-270171,2002-100478, 2002-100782) is preferred as enhancing the electroninjection/transportation capability and improving the film quality. Inthis case, the film thickness is generally at least 5 nm, preferably atleast 10 nm, and is generally at most 200 nm, preferably at most 100 nm.

The electron injection layer is formed by lamination on the lightemission layer or on the overlying hole inhibition layer, according to awet film formation method or a vacuum evaporation method.

The details of the wet film formation method are the same as those forthe hole injection layer and the light emission layer.

On the other hand, in case of the vacuum evaporation method, the vaporsource is put in the crucible or the metal boat arranged in a vacuumchamber, then the vacuum chamber is degassed with a vacuum pump to 10⁻⁴Pa or so, and the crucible or the metal boat is heated and the vaporsource is evaporated, whereby the intended electron injection layer isformed on the light emission layer, the hole inhibition layer or theelectron transport layer on the substrate disposed to face the crucibleor the metal boat.

Vapor deposition of alkali metal to give the electron injection layer isattained, using an alkali metal dispenser prepared by filling an alkalimetal chromate and a reducing agent in Nichrome. The dispenser is heatedin the vacuum chamber whereby the alkali metal chromate is reduced andthe alkali metal is thereby evaporated. In case of co-evaporation of anorganic electron-transporting material and an alkali metal, the organicelectron-transporting material is put in the crucible arranged insidethe vacuum chamber, then the vacuum chamber is degassed with a suitablevacuum pump to 10⁻⁴ Pa or so, and the crucible and the dispenser areheated for evaporation at the same time to thereby form the intendedelectron injection layer on the substrate arranged to face the crucibleand the dispenser.

In this, the two are co-deposited uniformly in the thickness directionof the electron injection layer, but may have a concentration profile inthe thickness direction.

[9] Cathode:

The cathode plays a role of injecting an electron into the layer on theside of the light emission layer (electron injection layer or lightemission layer). As the material for the cathode, the material for useof the above-mentioned anode may be used; however, for efficientelectron injection, preferred is a metal having a low work function.Suitable metals such as tin, magnesium, indium, calcium, aluminium orsilver or they alloys may be used. Specific examples arelow-work-function alloy electrodes of magnesium-silver alloy,magnesium-indium alloy, aluminium-lithium alloy, etc.

The thickness of the cathode is generally the same as that of the anode.

For the purpose of protecting the cathode formed of a low-work-functionmetal, a metal layer having a high work function and is stable to air ispreferably laminated on the cathode, whereby the stability of the devicecould increase. For this purpose, metals are used, such as aluminium,silver, copper, nickel, chromium, gold or platinum.

[10] Others:

In the above, an example of the organic electroluminescence elementhaving a layer constitution of FIG. 1 has been described; however, theorganic electroluminescence element of the invention may have any otherconstitution, not overstepping the sprit and the scope thereof. Forexample, not detracting from the performance, any other layer than thelayers described above may be provided between the anode and thecathode, and any layer therebetween may be omitted.

In the invention, the polymer compound of the invention may be used inthe hole transport layer, and in that manner, all the hole injectionlayer, the hole transport layer and the light emission layer can beformed by lamination according to a wet film formation method.Accordingly, a large-area display can be produced.

An opposite structure to FIG. 1 may also be employed, or that is, on thesubstrate, a cathode, an electron injection layer, a light emissionlayer, a hole injection layer and an anode may be laminated in thatorder; and as previously mentioned, the organic electroluminescenceelement of the invention may be arranged between two substrates of whichat least one has high transparency.

Further, the invention may employ a laminate structure comprising aplurality of the layer constructions shown in FIG. 1 (laminate structureof plural light emission units). In this case, in place of theinterlayer between the unit layer constructions (light emission units)(when the anode is ITO and the cathode is Al, in place of both the twolayers), for example, V₂O₅ or the like may be used as a chargegeneration layer (CGL), and this is favorable from the viewpoint of thecurrent efficiency and the drive voltage since the barrier between theunits may be reduced.

The invention is applicable to any of device structures where theorganic electroluminescence element is arranged as a single device or asan array, or device structures where the anode and the cathode arearranged as X-Y matrices.

<Organic EL Display and Organic EL Lighting>

The organic EL display and the organic EL light of the inventioncomprise the organic electroluminescence element of the invention asabove. The type and the structure of the organic EL display and theorganic EL lighting of the invention are not specifically defined; andthey can be constructed using the organic electroluminescence element ofthe invention and according to an ordinary method.

For example, the organic EL display and the organic EL lighting of theinvention can be constructed according to the method described in“Organic EL Displays” (Ohmsha, issued on Aug. 20, 2004, written by SeijiTokitoh, Chihaya Adachi, Hideyuki Murata).

EXAMPLES

The invention is described more concretely with reference to thefollowing Examples. However, the invention is not limited to thefollowing Examples, and the invention can be changed and modified in anydesired manner not overstepping the sprit and the scope thereof. Unlessotherwise specifically indicated, in the following description, dbameans dibenzylideneacetone, tBu means a t-butyl group, THF meanstetrahydrofuran, Me means a methyl group, Et means an ethyl group, iPrmeans an i-propyl group, Ph means a phenyl group, Ac means an acetylgroup, DMSO means dimethyl sulfoxide, TBAB means tetrabutylammoniumbromide, DME means dimethoxyethane, Tf₂O means trifluoromethanesulfonicacid anhydride, DMF means dimethylformamide, dppf means1,1′-diphenylphosphinoferrocene, NBS means N-bromosuccinimide.

Production Examples

Production Examples for the polymer compound of the invention are shownbelow.

[Production of Monomer]

Production Example 1

Potassium hydroxide was added to the compound 1 (10.0 g), the compound 2(16.3 g) and dimethyl sulfoxide (80 ml), and stirred at room temperaturefor 6 hours. Ethyl acetate (100 ml) and water (100 ml) were added to thereaction liquid, stirred, then processed for liquid-liquid separation;the aqueous layer was extracted with ethyl acetate (100 ml×twice); theorganic layers were combined, dried with magnesium sulfate and thenconcentrated. Further, this was purified through silica gel columnchromatography (n-hexane/ethyl acetate=10/1) to give the intendedproduct 1 (13.3 g).

Production Example 2

In a nitrogen flow, the product 1 (3.0 g), the compound 3 (1.44 g),sodium tert-butoxide (1.13 g) and toluene (50 ml) were stirred for 30minutes under heat at 60° C., thentris(dibenzylidene)dipalladium(0)/chloroform complex (0.09 g) andtri-tert-butyl phosphine (0.07 g) were added thereto and stirred for 3hours with heating under reflux. This was left cooled to roomtemperature, then toluene (100 ml) and water (100 ml) were added to thereaction liquid, stirred, processed for liquid-liquid separation; andthe aqueous layer was extracted with toluene (100 ml×twice), the organiclayers were combined, dried with magnesium sulfate, and concentrated.Further, this was purified through silica gel column chromatography(n-hexane/ethyl acetate=10/1) to give the intended product 2 (3.4 g).

Production Example 3

In a nitrogen flow at −5° C., NBS (30 ml) dissolved in DMF was dropwiseadded to the product 2 (3.4 g) and DMF (100 ml), and stirred for 2 hoursat the temperature. Ethyl acetate (100 ml) and water (100 ml) were addedto the reaction liquid, stirred, processed for liquid-liquid separation;and the aqueous layer was extracted with ethyl acetate (100 ml×twice),the organic layers were combined, dried with magnesium sulfate, andconcentrated. Further, this was purified through silica gel columnchromatography (n-hexane/ethyl acetate=10/1) to give the intendedproduct 3 (2.3 g).

Production Example 4

In a nitrogen flow, pyrene (10.11 g) and dimethoxyethane (400 ml) werestirred with cooling at 0° C. in an ice bath, and bromine (15.18 g)dissolved in dimethoxyethane (50 ml) was dropwise added thereto, heatedup to room temperature and stirred for 8 hours, and then left overnight.The precipitated crystal was taken out through filtration, washed withethanol by suspension, and recrystallized from toluene to give theintended product 4 (mixture of 1,6-dibromopyrene and 1,8-dibromopyrene)(5.8 g).

¹H NMR (CDCl₃, 400 MHz)

1,8-dibromopyrene

δ 8.53 (2, 2H), 8.28 (d, 2H, J=8.40), 8.05 (d, 2H, J=8.00), 8.04 (s, 2H)

1,6-dibromopyrene

δ 8.47 (d, 2H, J=9.60), 8.27 (d, 2H, J=8.40), 8.13 (d, 2H, J=9.20), 8.06(d, 2H, J=8.40)

Production Example 5

Potassium fluoride (23.01 g) was put into a reactor, and under reducedpressure, the system was made to have a nitrogen atmosphere throughrepeated drying under heat and purging with nitrogen.3-Nitrophenylboronic acid (6.68 g), 4-bromo-benzocyclobutene (7.32 g)and dewatered tetrahydrofuran (50 ml) were put into it and stirred.Tris(dibenzylideneacetone)dipalladium/chloroform complex (0.21 g) wasadded thereto, and the system was further fully purged with nitrogen,tri-t-butyl phosphine (0.47 g) was added to it. After the addition, thiswas stirred as it was. After the reaction, water was added to thereaction liquid, and extracted with ethyl acetate. The resulting organiclayer was washed twice with water, dewatered and dried with sodiumsulfate added thereto, and concentrated. The crude product was purifiedthrough silica gel column chromatography (hexane/ethyl acetate) to givethe intended product 5 (8.21 g).

Production Example 6

The product 5 (8.11 g), tetrahydrofuran (36 ml), ethanol (36 ml) and 10%Pd/C (1.15 g) were put in a reactor, and stirred under heat at 70° C.Hydrazine monohydrate (10.81 g) was gradually and dropwise added to it.After reacted for 2 hours, this was left cooled, the reaction liquid wasfiltered through Celite and the filtrate was concentrated. Ethyl acetatewas added to the filtrate, washed with water, and the organic layer wasconcentrated. The resulting crude product was purified through silicagel column chromatography (hexane/ethyl acetate) to give the intendedproduct 6 (4.90 g).

Production Example 7

2-Nitrofluorene (25.0 g), 1-bromohexane (58.61 g), tetrabutylammoniumbromide (7.63 g) and dimethyl sulfoxide (220 ml) were put in a reactor,and aqueous 17 M sodium hydroxide solution (35 ml) was gradually anddropwise added thereto, and reacted at room temperature for 3 hours.Ethyl acetate (200 ml) and water (100 ml) were added to the reactionliquid, stirred, processed for liquid-liquid separation, and the aqueouslayer was extracted with ethyl acetate. The organic layers werecombined, dried with magnesium sulfate, and concentrated. The resultingcrude product was purified through silica gel column chromatography(hexane/ethyl acetate) to give the intended product 7 (44.0 g).

Production Example 8

10% Pd/C (8.6 g) was added to the product 7 (44.0 g), tetrahydrofuran(120 ml) and ethanol (120 ml), and stirred under heat at 50° C.Hydrazine monohydrate (58.0 g) was gradually and dropwise added to it,and reacted for 3 hours at the temperature. The reaction liquid was leftcooled, filtered through Celite under pressure, and the filtrate wasconcentrated, methanol was added to the residue, and the precipitatedcrystal was collected through filtration and dried to give the intendedproduct 8 (34.9 g).

Production Example 9

Dichlorobis(acetonitrile)palladium(II) (212 mg, 0.03 equivalents) andcopper iodide (104 mg, 0.02 equivalents) were put into a 200-mLfour-neck flask with nitrogen kept introduced thereinto, and dioxane (75mL) previously deaerated by nitrogen bubbling thereinto was put into itand stirred. Tri-t-butyl phosphine (331 mg, 0.06 equivalents) was addedto this liquid, and stirred for 15 minutes at room temperature.Di-1-propylamine (3.31 g, 1.2 equivalents), 4-bromobenzocyclobutene(5.00 g, 1.0 equivalent) and 1,7-octadiyne (20.3 g, 7.0 equivalents)were added to the solution, and reacted at room temperature for 9 hours.The resulting reaction mixture was processed under a reduced pressure of400 Pa and at a bath temperature of 60° C. to remove the light volatilefraction through vaporization, then saturated saline water (50 mL) and 1N hydrochloric acid (5 mL) were added thereto, and extracted three timeswith ethyl acetate (30 mL), and the resulting ethyl acetate layer waswashed twice with saturated saline water (30 mL). The ethyl acetatelayer was concentrated to give a crude product (7.7 g). The crudeproduct was purified through silica gel column chromatography (solvent:n-hexane/ethyl acetate mixed solvent) to give the intended product 9(2.78 g; yield, 48.0%; purity after analyzed through gas chromatography,95.4%) as a colorless oil.

Production Example 10

M-iodonitrobenzene (3.64 g, 1.1 equivalents), potassium carbonate (5.06g, 2.75 equivalents), copper iodide (111 mg, 0.044 equivalents),triphenyl phosphine (307 g, 0.088 equivalents) and 5% Pd/C (623 mg,0.022 equivalents as Pd) were put into a 100-mL four-neck flask withnitrogen kept introduced thereinto, and a mixed solvent ofdimethoxyethane/water (1/1 by volume) (95 mL) previously deaerated bynitrogen bubbling thereinto was put into it and stirred at roomtemperature for 1 hour. A solution of the product 9 (2.77 g, 1.0equivalent) dissolved in dimethoxyethane (2 mL) was added to the liquid,and reacted under heat in a bath at 70° C. (inner temperature, 63° C.)for 7 hours. The resulting reaction mixture was filtered through Celite,concentrated with an evaporator, and 1 N hydrochloric acid (25 mL) wasadded to it, extracted three times with ethyl acetate (30 mL), and theresulting ethyl acetate layer was washed three times with saturatedsaline water (20 mL). The ethyl acetate layer was concentrated, and theresulting crude product was recrystallized from a mixed solvent of ethylacetate/n-hexane to give the intended product 10 (2.50 g; yield, 57.1%;purity after analyzed through gas chromatography, 99.5%) as a thin paleyellow acicular crystal.

Production Example 11

The product 10 (2.31 g), tetrahydrofuran (15 mL) and ethanol (15 mL)were put into a 100-mL eggplant-type flask and dissolved. As ahydrogenation catalyst, Raney nickel (1.07 g, Nikko Rika's R-200) wasadded to the solution, purged three times with hydrogen, and inhydrogen, this was reacted at room temperature for 35 hours. Thereaction liquid was filtered through Celite and concentrated to give acrude product (2.8 g). The crude product was purified through silica gelcolumn chromatography (solvent: n-hexane/ethyl acetate mixed solvent) togive the intended product 11 (1.72 g; yield, 80.1%; purity afteranalyzed through liquid chromatography, 99.1%) as a white acicularcrystal.

Production Example 12

In a nitrogen flow, 3-bromostyrene (5.0 g), 3-nitrophenylboronic acid(5.5 g), toluene/ethanol (80 ml/40 ml) and aqueous 2 M sodium carbonatesolution were put into a reactor, and stirred and deaerated under heatat 60° C. for 30 minutes. Tetrakis(triphenylphosphine)palladium (0.95 g)was added to it and refluxed for 6 hours. After left cooled to roomtemperature, methylene chloride (100 ml) and water (100 ml) were addedto the reaction liquid, stirred, processed for liquid-liquid separation,and the aqueous layer was extracted with methylene chloride. The organiclayers were combined, dried with magnesium sulfate, and concentrated.The resulting crude product was purified through silica gel columnchromatography (n-hexane/methylene chloride) to give the intendedproduct 12 (5.5 g).

Production Example 13

In a nitrogen flow, the product 12 (2.5 g), acetic acid (60 ml), ethanol(60 ml), 1 N hydrochloric acid (2 ml), water (8 ml) and reduced iron(12.4 g) were put in a reactor and heated under reflux for 1 hour. Thereaction liquid was filtered at room temperature, ethyl acetate (100 ml)and water (100 ml) were added thereto, stirred, then neutralized withaqueous saturated sodium hydrogencarbonate solution, processed forliquid-liquid separation, and the aqueous layer was extracted with ethylacetate. The organic layers were combined, dried with magnesium sulfate,and concentrated. The resulting crude product was purified throughsilica gel column chromatography (n-hexane/ethyl acetate) to give theintended product 13 (2.1 g).

Production Example 14

In a nitrogen flow, 1,2-dibromobenzene (21.0 g), 3-methoxyphenylboronicacid (29.9 g), toluene/ethanol (147 ml/147 ml) and aqueous 2 M sodiumcarbonate solution (295 ml) were put in a reactor, and deaerated withstirring under heat at 60° C. for 30 minutes.Tetrakis(triphenylphosphine)palladium (6.17 g) was added thereto, andrefluxed for 6 hours. After this was left cooled to room temperature,water was added thereto, stirred, processed forliquid-liquid-separation, and the aqueous layer was extracted withtoluene. The organic layers were combined, dried with magnesium sulfate,and concentrated. The resulting crude product was purified throughsilica gel column chromatography (n-hexane/methylene chloride) to givethe intermediate 1 (15.5 g).

The intermediate 1 (15.5 g) was dissolved in methylene chloride (70 ml),and concentrated sulfuric acid (1.4 g) was added thereto. Iron chloride(21.6 g) was gradually added thereto little by little. After reacted for7 hours, methylene chloride (100 ml) was added to it, which was put intocold methanol, and the precipitated crystal was collected throughfiltration. The crude crystal was dissolved in methylene chloride (250ml), washed with 1 N hydrochloric acid (100 ml), and the organic layerwas filtered through Celite, concentrated, and washed with methanol bysuspension to give the intermediate (7.41 g).

The intermediate 2 (7.41 g) was dissolved in methylene chloride (110ml), and with cooling with ice, boron trifluoride (1 M methylenechloride solution, 65 ml) was added thereto and stirred for 3 hours.Water was added to the reaction liquid, and extracted with ethylacetate. The organic layer was washed with water, dried with magnesiumsulfate, and concentrated. The precipitated crystal was washed with amethylene chloride/ethyl acetate (5/1) solution by suspension to givethe intermediate 3 (6.58 g).

Methylene chloride (130 ml) was added to the intermediate 3 (6.58 g),and trifluoromethanesulfonic acid anhydride (17.8 g) was added thereto.Further, pyridine (4.4 g) was gradually added, and reacted at roomtemperature for 5 hours. The precipitated crystal was collected throughfiltration, washed with water, washed with methanol by suspension, andwashed twice with methylene chloride/methanol (1/9) by suspension togive the intermediate 4 (5.9 g).

In a nitrogen flow, the intermediate 4 (3.88 g), 4-nitrophenylboronicacid (2.72 g), toluene/ethanol (48 ml/48 ml), and aqueous 2 M sodiumcarbonate solution (24 ml) were put in a reactor, and stirred anddeaerated for 30 minutes with heating at 40° C.Tetrakis(triphenylphosphine)palladium (0.53 g) was added thereto andrefluxed for 6 hours. After left cooled to room temperature, water wasadded to it and stirred, and the precipitated crystal was collectedthrough filtration. This was washed with ethyl acetate by suspension togive the intermediate 5 (2.35 g).

The intermediate 5 (2.35 g) was dissolved in N,N-dimethylformamide (195ml), 5% Pd/C (1.06 g) was added thereto, the system was purged withhydrogen, and in hydrogen, this was reacted for 4 hours at 70° C. Thereaction liquid was purged with nitrogen, filtered through Celite, thefiltrate was concentrated to about 30 ml, and added to methanol. Waterwas added to it, and the precipitated crystal was collected throughfiltration to give the intended product 14 (1.03 g).

Production Example 15

The product 14 (1.82 g), 2-bromo-9,9-dihexylfluorene (3.7 g), sodiumtert-butoxide (0.94 g) and toluene (25 ml) were put in a reactor, thesystem was fully purged with nitrogen and heated up to 50° C. (solutionA).

On the other hand, diphenylphosphinoferrocene (0.20 g) was added to atoluene (4 ml) solution oftris(dibenzylideneacetone)palladium/chloroform complex (0.09 g), andheated up to 50° C. (solution B).

In a nitrogen flow, the solution B was added to the solution A, andreacted for 5 hours with heating under reflux. The absence of thestarting materials was confirmed, and tetrahydrofuran was added to it,filtered through Celite, and the filtrate was concentrated and purifiedthrough silica gel column chromatography (n-hexane/ethyl acetate). Theresulting crude crystal was washed by suspension with n-hexane andmethanol to give the intended product 15 (1.34 g).

Production Example 16

The product 15 (0.50 g), 3-(3-bromophenyl)benzocyclobutene (0.63 g),sodium tert-butoxide (0.26 g) and toluene (15 ml) were put in a reactor,the system was fully purged with nitrogen and heated up to 50° C.(solution A).

On the other hand, diphenylphosphinoferrocene (0.05 g) was added to atoluene (1 ml) solution oftris(dibenzylideneacetone)palladium/chloroform complex (0.02 g), andheated up to 50° C. (solution B).

In a nitrogen flow, the solution B was added to the solution A, andreacted for 6 hours with heating under reflux. The absence of thestarting materials was confirmed, and tetrahydrofuran was added to it,filtered through Celite, and the filtrate was concentrated and purifiedthrough silica gel column chromatography (n-hexane/ethyl acetate) togive the intended product 16 (0.12 g).

Production Example 17

In a nitrogen flow, the product 12 (2.8 g), 4-bromobenzocyclobutene(3.65 g), potassium carbonate (2.73 g), (n-C₄H₉)₄ Br (2.67 g), dewateredDMF (76 ml) and a palladium catalyst Pd₂(diphenyl-Cl₂ NOH)₂ Cl₂ (15.1mg) were reacted at 130° C. for 8 hours, then ethyl acetate (100 ml) andwater (100 ml) were added to the reaction liquid at room temperature,stirred, processed for liquid-liquid separation, and the aqueous layerwas extracted twice with ethyl acetate (100 ml). The organic layers werecombined, dried with magnesium sulfate, and concentrated. Further, thiswas purified through silica gel column chromatography (n-hexane/ethylacetate=10/1) to give the intended product 17 (trans, 1.7 g; LC, 98%).

Production Example 18

In a nitrogen flow, the product 17 (1.6 g), acetic acid (30 ml), ethanol(30 ml), hydrochloric acid (1 N, 1 ml) water (4 ml) and reduced iron(5.5 g) were refluxed for 2 hours. The reaction liquid was filtered atroom temperature, ethyl acetate (100 ml) and water (100 ml) were addedthereto, stirred, neutralized with aqueous saturated sodiumhydrogencarbonate solution, processed for liquid-liquid separation, andthe aqueous layer was extracted twice with ethyl acetate (50 ml). Theorganic layers were combined, dried with magnesium sulfate, andconcentrated. Further, this was purified through silica gel columnchromatography (n-hexane/ethyl acetate=3/1) to give the intended product18 (1.3 g).

Production Example 19

3-Bromophenylboronic acid (10.0 g), m-diiodobenzene (8.21 g), sodiumcarbonate (15.83 g), toluene (150 mL), ethanol (150 mL) and water (75mL) were put in a reactor, deaerated under reduced pressure, and in anitrogen atmosphere, tetrakis(triphenylphosphine)palladium(0) (1.726 g)was added thereto. After stirred at 80° C. for about 4.5 hours, this wasleft cooled to room temperature. Water was added to the reaction liquid,extracted with a mixed solvent of ethyl acetate/hexane, and theresulting organic layer was concentrated. The crude product was purifiedthrough silica gel column chromatography (hexane) to give the intendedproduct 19 (7.39 g).

Production Example 20

In a nitrogen atmosphere, p-dibromobenzene (50 g) and THF (740 mL) wereput in a reactor, and cooled to −78° C. 1.55 M n-butyllithium/hexanesolution (125.7 mL) was dropwise added thereto, taking about 40 minutes.Further, this was stirred for about 1 hour, and anthraquinone (15.44 g)was added thereto. This was further stirred for about 3 hours, and thenheated up to room temperature, taking about 1 hour. Further, this wasstirred for about 3.5 hours, then water (100 mL) was added thereto, andTHF was evaporated away under reduced pressure. This was extracted withethyl acetate, the organic layer was washed with water, dried withanhydrous sodium sulfate, filtered, and concentrated. The resultingcrude product was washed by suspension with a mixed solvent of methylenechloride/hexane, and washed with methanol by suspension to give theintended product 20 (25.8 g).

Production Example 21

In a nitrogen atmosphere, the product 20 (25.7 g), acetic acid (400 mL)and zinc powder (27.4 g) were put in a reactor, and heated under reflux.After 8 hours, acetic acid (190 ml) was additionally added to it, andheated under reflux for about 8 hours. After left cooled to roomtemperature, water (400 mL) was added to it, the solid was collectedthrough filtration and washed with water. The resulting solid wassuspended in methylene chloride (2.5 L), the insoluble matter wasremoved through filtration, and the filtrate was concentrated. Theresulting crude product was dissolved in methylene chloride (3 L), andpurified through silica gel column chromatography (methylene chloride),then washed by suspension with methylene chloride, and washed bysuspension with chloroform to give the intended product 21 (10.7 g).

Production Example 22

In a nitrogen atmosphere, m-dibromobenzene (25 g) and THF (370 mL) wereput in a reactor, and cooled to −78° C. 1.6 M n-butyllithium/hexanesolution (61 mL) was dropwise added to it, taking about 10 min. Further,this was stirred for about 1 hour, and anthraquinone (7.72 g) was addedthereto. This was further stirred for about 1 hour, and then heated upto room temperature, taking about 1 hour. Further, this was stirred forabout 3.5 hours, then water (150 mL) was added thereto, and THF wasevaporated away under reduced pressure. This was extracted with ethylacetate, the organic layer was washed with water, dried with anhydroussodium sulfate, filtered, and concentrated. The resulting crude productwas washed by suspension with a mixed solvent of methylenechloride/hexane to give the intended product 22 (17.4 g).

Production Example 23

In a nitrogen atmosphere, the product 22 (17.4 g), acetic acid (242 mL)and zinc powder (18.6 g) were put in a reactor, and heated under reflux.After 10.5 hours, this was left cooled to room temperature, water (250mL) was added to it, the solid was collected through filtration andwashed with water. The resulting solid was suspended in methylenechloride (500 mL), the insoluble matter was removed through filtration,the filtrate was concentrated, and washed with hexane by suspension. Theresulting crude product was dissolved in methylene chloride (200 mL),and purified through silica gel column chromatography (methylenechloride). The resulting solid was completely dissolved in1,2-dimethoxyethane (102 mL) with heating under reflux, and graduallycooled to room temperature. The precipitated solid was collected throughfiltration to give the intended product 23 (3.7 g).

Production Example 24

1,3,5-Tribromobenzene (22 g), 3-biphenylboronic acid (4.95 g), toluene(110 ml) and ethanol (100 ml) were put in a reactor, and deaerated bybubbling with nitrogen for 10 minutes. Sodium carbonate (7.9 g) andwater (38 ml) were put in a different container, and with stirring, thiswas deaerated by bubbling with nitrogen. The aqueous solution was addedto the previous reactor, and immediatelytetrakis(triphenylphosphine)palladium(0) (866 mg) was added thereto,heated, and kept heated under reflux. After the reaction, water wasadded to the reaction liquid, and extracted with toluene. The resultingorganic layer was dewatered and dried with sodium sulfate added thereto,and concentrated. The crude product was purified through silica gelcolumn chromatography (hexane/dichloromethane) to give the intendedproduct 24 (7.51 g).

Production Example 25

The product 24 (7.0 g), bis(pinacolato)diboron (11.68 g), potassiumacetate (9.71 g), and dimethylformamide (100 ml) were put in a reactor,and stirring it was started with bubbling with nitrogen. After 15minutes, the nitrogen bubbling was changed to flowing, and PdCl₂(dppf).CH₂ Cl₂ (660 mg) was added thereto and heated up to 80° C. Afterthe reaction, this was left cooled, washed by extraction withdichloromethane and water, dried with sodium sulfate, and concentrated.The resulting crude product was purified through column chromatography(hexane/ethyl acetate) to give the intended product 25 (10 g).

Production Example 26

The product 25 (5.8 g), 4-bromoiodobenzene (7.5 g), toluene (72 ml) andethanol (72 ml) were put in a reactor, and deaerated by bubbling withnitrogen for 10 minutes. Sodium carbonate (7.6 g) and water (36 ml) wereput in a different container, and with stirring, this was deaerated bybubbling with nitrogen. The aqueous solution was added to the previousreactor, and immediately tetrakis(triphenylphosphine)palladium(0) (1.0g) was added thereto, heated, and kept heated under reflux. After thereaction, water was added to the reaction liquid, and extracted withdichloromethane. The resulting organic layer was dewatered and driedwith sodium sulfate added thereto, and concentrated. The crude productwas purified through silica gel column chromatography (hexane/ethylacetate) to give the intended product 26 (3.9 g).

Production Example 27

Toluene (100 ml), ethanol (50 ml), 4-bromophenylboronic acid (9.99 g),1,3-diiodobenzene (8.41 g), sodium carbonate (8.41 g) and water (35 ml)were put in a reactor, and by bubbling with nitrogen, the system wasmade to have fully a nitrogen atmosphere, and stirred.Tetrakis(triphenylphosphine)palladium (0.884 g) was added to it, andheated, and kept heated under reflux for 7 hours.

After the reaction, water was added to the reaction liquid and extractedwith toluene. The resulting organic layer was washed twice with water,and dewatered and dried with sodium sulfate added thereto, andconcentrated. The crude product was purified through silica gel columnchromatography (hexane/toluene) to give the intended product 27 (3.54g).

Production Example 28

9,9-Dihexylfluorene-2,7-diboronic acid (3.0 g, 7.1 mmol),4-bromoidodobenzene (4.42 g, 15.6 mmol), toluene (45 ml) and ethanol (45ml) were put in a reactor, and the system was made to have a nitrogenatmosphere by repeated nitrogen purging under reduced pressure. Further,the system was fully purged with nitrogen, andtetrakis(triphenylphosphine)palladium (0.54 g, 0.5 mmol) was added toit, and an aqueous solution (22 ml) of deaerated sodium carbonate (4.52g, 43 mmol) was added thereto and reacted for 6 hours. After thereaction, water was added to the reaction liquid and extracted withtoluene. The resulting organic layer was washed twice with water, anddewatered and dried with sodium sulfated added thereto, and thenconcentrated. The crude product was washed with n-hexane, purifiedthrough silica gel column chromatography (hexane/methylene chloride),and washed by suspension with methylene chloride/methanol to give theintended product 28 (3.15 g).

Production Example 29

Dichloromethane (200 ml) was put in a reactor in a nitrogen atmosphere,and N-phenylcarbazole (2.29 g) and bis(pyridine)iodoniumtetrafluoroborate (7.76 g) were dissolved therein. Next, with coolingwith ice, trifluoromethanesulfonic acid (1.75 ml) was dropwise addedthereto, and with heating up to room temperature, this was stirred forone full day. After the reaction, aqueous 0.5 M sodium thiosulfatesolution was added to the reaction liquid and extracted withdichloromethane. The resulting organic layer was washed with water,dewatered and dried with sodium sulfate added thereto, and concentrated.Methanol was added to a dichloromethane solution of the crude productfor reprecipitation, and the precipitated product was washed underreflux of methanol to give the intended product 29 (4.00 g).

Production Example 30

The product 29 (4.00 g), p-bromophenylboronic acid (3.05 g), toluene (30ml), ethanol (15 ml) and aqueous 2.6 M sodium carbonate solution (20 ml)were put in a reactor, and this was degassed into vacuum with vibratingit with an ultrasonic washer, and the system was purged with nitrogen.Tetrakis(triphenylphosphine)palladium (0.27 g) was added to it, andstirred under heat at 75° C. for 3 hours. After the reaction, water wasadded to the reaction liquid, and extracted with dichloromethane. Theresulting organic layer was dewatered and dried with sodium sulfateadded thereto, and concentrated. The crude product was isolated throughsilica gel column chromatography (hexane/dichloromethane) and purifiedthrough recrystallization from hot dimethoxyethane to give the intendedproduct 30 (2.25 g).

Production Example 31

Diethyl ether (100 ml) was put in a reactor in a nitrogen atmosphere,3,3′-dibromo-1,1′-biphenyl (9.00 g) was dissolved therein, and cooled to−78° C. 1.6 M n-butyllithium/hexane solution (40 ml) was dropwise addedto it, taking 15 minutes, then stirred at −78° C. for 1 hour, heated upto 0° C., and further stirred for 2 hours. On the other hand, in adifferent container, trimethyl borate (33 ml) was dissolved in diethylether (160 ml) in a nitrogen atmosphere, and cooled to −78° C. toprepare a solution. The above-mentioned mixed liquid was dropwise putinto the solution, taking 45 minutes, and then stirred for 4 hours withgradually restoring the liquid temperature to room temperature. Afterthe reaction, 3 N hydrochloric acid (144 ml) was gradually added to thereaction liquid at 0° C., stirred for 4 hours at room temperature, andthe white precipitate was collected through a 3G glass funnel. This waswashed with water and diethyl ether, and dried to give the intendedproduct 31 (3.16 g).

Production Example 32

The product 31 (2.85 g), p-iodobromobenzene (6.68 g), toluene (40 ml),ethanol (20 ml) and aqueous 2.6 M sodium carbonate solution (30 ml) wereput in a reactor, and this was degassed into vacuum with vibrating itwith an ultrasonic washer, and the system was purged with nitrogen.Tetrakis(triphenylphosphine)palladium (0.41 g) was added to it, andstirred under heat at 75° C. for 6 hours. After the reaction, water andtoluene were added to the reaction liquid, the toluene layer was washedwith 0.1 N hydrochloric acid and water, then dewatered and dried withsodium sulfate added thereto, and concentrated. The crude product waspurified through silica gel column chromatography (hexane/chloroform) togive the intended product 32 (3.01 g).

[Production of Polymer Compound]

Production Example 33

In a nitrogen flow, aqueous 20% tetraethylammonium hydroxide solution(20 ml) was added to a solution of the compound 4 (2.512 g), the product3 (0.302 g), the compound 5 (1.033 g), the product 4 (0.792 g;1,8-dibromopyrene/1,6-dibromopyrene=37/63) and toluene (40 ml), andtetrakis(triphenylphosphine)palladium(0) (0.058 g) was added to it, andstirred with heating under reflux for 8 hours. After left cooled, thereaction liquid was added to ethanol, and the precipitated crude polymer1 was collected through filtration and dried. In a nitrogen flow,aqueous 20% tetraethylammonium hydroxide solution (50 ml) was added to asolution of the crude polymer 1, bromobenzene (0.140 g) and toluene (100ml), and tetrakis(triphenylphosphine)palladium(0) (0.058 g) was added toit, and stirred from 2.5 hours with heating under reflux. Subsequently,phenylboronic acid (0.610 g) was added thereto, and stirred for 6 hourswith heating under reflux. After left cooled, toluene and water wereadded thereto, the organic layer was concentrated into 50 ml, ethanolwas added, and the precipitated crude polymer was collected throughfiltration and dried, and purified through a silica gel column with adeveloping solvent of toluene and tetrahydrofuran. From thetetrahydrofuran solution, the product was reprecipitated in ethanol,collected through filtration and dried to give the intended polymer 1(2.20 g).

Weight-Average Molecular Weight (Ms)=26,000

Number-Average Molecular Weight (Mn)=13,000

Dispersity (Mw/Mn)=2.0

Production Example 34

Aniline (1.98 g, 21.3 mmol), the product 6 obtained in ProductionExample 6 (0.22 g, 1.1 mmol), 2,7-dibromo-9,9-dihexylfluorene (5.52 g,11.2 mmol), sodium tert-butoxide (6.90 g, 71.8 mmol) and toluene (51 ml)were put in a reactor, and the system was fully purged with nitrogen,and heated up to 50° C. (solution A). Tri-t-butyl phosphine (0.37 g, 1.8mmol) was added to a toluene (15 ml) solution oftris(dibenzylideneacetone)dipalladium/chloroform complex (0.23 g, 0.2mmol), and heated up to 50° C. (solution B). In a nitrogen flow, thesolution B was added to the solution A, and reacted for 1 hour withheating under reflux. The absence of the starting materials wasconfirmed, and 4,4′-dibromobiphenyl (3.29 g, 10.5 mmol) was additionallyadded to it. After this was heated under reflux for 1 hour, the start ofpolymerization was confirmed; and 4,4′-dibromobiphenyl (0.07 g, 0.2mmol) was additionally added to it at hourly intervals for a total ofthree times (0.21 g in total). After the total amount of4,4′-dibromobiphenyl was added, this was further heated under reflux for30 hours, then the reaction liquid was left cooled, and the reactionliquid was dropwise added to an aqueous ethanol solution (ethanol 300ml+water 50 ml), in which a crude polymer 2 was thereby precipitated.

The resulting crude polymer 2 was dissolved in toluene (140 ml), andbromobenzene (0.70 g, 4.5 mmol) and sodium tert-butoxide (3.45 g, 35.9mmol) were added thereto, then the system was fully purged withnitrogen, and heated up to 50° C. (solution C). Tri-t-butyl phosphine(0.19 g, 0.9 mmol) was added to a toluene (8 ml) solution oftris(dibenzylideneacetone)dipalladium/chloroform complex (0.11 g, 0.1mmol), and heated up to 50° C. (solution D). In a nitrogen flow, thesolution D was added to the solution C, and reacted for 2 hours withheating under reflux. A toluene (2 ml) solution of N,N-diphenylamine(3.80 g, 22.5 mmol) was added to the reaction liquid, and furtherreacted for 6 hours with heating under reflux. The reaction liquid wasleft cooled, and dropwise put into an aqueous ethanol solution (ethanol300 ml+50 ml) to give a crude polymer 2 of which the terminal residueswere capped.

The crude polymer 2 with capped terminal residues was dissolved intoluene, and reprecipitated in acetone, and the formed polymer wascollected through filtration. The resulting polymer was dissolved intoluene, washed with diluted hydrochloric acid, and reprecipitated inammonia-containing ethanol. The polymer collected through filtration waspurified twice through column chromatography to give the intendedpolymer 2 (1.38 g).

Weight-Average Molecular Weight (Ms)=67850

Number-Average Molecular Weight (Mn)=35400

Dispersity (Mw/Mn)=1.92

Production Example 35

The product 8 (3.64 g, 10.4 mmol) obtained in Production Example 8, theproduct 6 (0.51 g, 2.6 mmol) obtained in Production Example 6,4,4′-dibromobiphenyl (2.03 g, 13 mmol), sodium tert-butoxide (2.88 g,30.0 mmol) and toluene (20 ml) were put in a reactor, and the system wasfully purged with nitrogen and heated up to 50° C. (solution A).

On the other hand, tri-t-butyl phosphine (0.210 g, 0.104 mmol) was addedto a toluene (15 ml) solution oftris(dibenzylideneacetone)dipalladium/chloroform complex (0.148 g,0.0143 mmol), and heated up to 50° C. (solution B).

In a nitrogen flow, the solution B was added to the solution A, andreacted for 1 hour with heating under reflux. The absence of thestarting materials was confirmed, and 4,4′-dibromobiphenyl (1.91 g, 6.1mmol) was additionally added to it. After this was heated under refluxfor 1 hour, the start of polymerization was confirmed; and4,4′-dibromobiphenyl (0.041 g, 0.13 mmol) was additionally added to it,and further reacted for 1 hour with heating under reflux. The reactionliquid was left cooled, and dropwise put into methanol (200 ml) to givea crude polymer 3.

The resulting crude polymer 3 was dissolved in toluene (200 ml), andbromobenzene (2.04 g, 13 mmol) and sodium tert-butoxide (1.50 g, 16mmol) were added thereto, then the system was fully purged withnitrogen, and heated up to 50° C. (solution C).

On the other hand, tri-t-butyl phosphine (0.026 g, 13 mmol) was added toa toluene (10 ml) solution oftris(dibenzylideneacetone)dipalladium/chloroform complex (0.108 g, 10.4mmol), and heated up to 50° C. (solution D).

In a nitrogen flow, the solution D was added to the solution C, andreacted for 2 hours with heating under reflux. A toluene (2 ml) solutionof N,N-diphenylamine (3.82 g, 22.6 mmol) was added to the reactionliquid, and further reacted for 8 hours with heating under reflux. Thereaction liquid was left cooled, and dropwise put into methanol to givea crude end-capped polymer 3.

The crude end-capped polymer 3 was dissolved in toluene, andreprecipitated in acetone, and the formed polymer was collected throughfiltration. The resulting polymer was dissolved in toluene, washed withdiluted hydrochloric acid, and reprecipitated in ammonia-containingethanol. The polymer collected through filtration was purified throughcolumn chromatography to give the intended polymer 3 (1.01 g). Theweight-average molecular weight and the number-average molecular weightof the polymer 3 were measured, and were as follows:

Weight-Average Molecular Weight (Ms)=43300

Number-Average Molecular Weight (Mn)=26400

Dispersity (Mw/Mn)=1.64

Production Examples 36 to 41

Intended polymers 4 to 9 were produced according to the productionmethod of Production Example 35 but changing the monomers (the product6, the product 8 and 4,4′-dibromobiphenyl) to the compounds shown inTable 1 below. The thus-obtained polymers are shown in Table 1.

TABLE 1 Production Amount of Amount of Example Polymer FluorenamineAr^(a1) Br—Ar^(a1)—Br 35 3  3.64 g

 3.98 g 36 4  7.5 g

 7.95 g 37 5  2.99 g

 4.43 g 38 6 1.485 g

2.425 g 39 7 0.863 g

1.680 g 40 8  1.06 g

1.776 g 41 9 0.875 g

 3.0 g Production Amount of Yield of Example Ar^(a2) Ar^(a2)—NH₂ iPolymer Mw Mn Mw/Mn 35

 0.51 g 0.8    1.01 g 43300 26400 1.6 36

 0.22 g 0.95   1.20 g 35000 19000 1.8 37

 0.09 g 0.95   0.87 g 39000 24400 1.6 38

 0.17 g 0.83   0.27 g 68000 27400 2.5 39

0.111 g 0.81   0.88 g 25000 11900 2.1 40

0.046 g 0.9272 0.921 g 24000 11800 2   41

 0.7 g 0.41   1.9 g 47900 29500 1.6

Production Example 42

The product 8 (7.5 g, 21.5 mmol) obtained in Production Example 8, theproduct 6 (0.22 g, 1.1 mmol) obtained in Production Example 6,4,4′-dibromostilbene (3.82 g, 11.3 mmol), sodium tert-butoxide (6.95 g,72.3 mmol) and toluene (120 ml) were put in a reactor, and the systemwas fully purged with nitrogen and heated up to 50° C. (solution A).

On the other hand, tri-t-butyl phosphine (0.33 g, 0.45 mmol) was addedto a toluene (5 ml) solution oftris(dibenzylideneacetone)dipalladium/chloroform complex (0.06 g, 0.06mmol), and heated up to 50° C. (solution B).

In a nitrogen flow, the solution B was added to the solution A, andreacted for 3 hours with heating under reflux. The absence of thestarting materials was confirmed, and 4,4′-dibromobiphenyl (3.31 g, 10.6mmol) was additionally added to it. After this was heated under refluxfor 1.5 hours, the start of polymerization was confirmed; and4,4′-dibromobiphenyl (0.07 g, 0.2 mmol) was additionally added to it atintervals of 1.5 hours for a total of 3 times. After the total amount of4,4′-dibromobiphenyl was added, this was further heated under reflux for1 hour, and the reaction liquid was left cooled, and dropwise put intomethanol (300 ml) to give a crude polymer 10 through crystallization.

The resulting crude polymer 10 was dissolved in toluene (180 ml), andbromobenzene (0.71 g, 4.5 mmol) and sodium tert-butoxide (3.5 g, 36.4mmol) were added thereto, then the system was fully purged withnitrogen, and heated up to 50° C. (solution C).

On the other hand, tri-t-butyl phosphine (0.18 g, 0.9 mmol) was added toa toluene (10 ml) solution oftris(dibenzylideneacetone)dipalladium/chloroform complex (0.12 g, 0.1mmol), and heated up to 50° C. (solution D).

In a nitrogen flow, the solution D was added to the solution C, andreacted for 2 hours with heating under reflux. A toluene (2 ml) solutionof N,N-diphenylamine (3.82 g, 22.6 mmol) was added to the reactionliquid, and further reacted for 8 hours with heating under reflux. Thereaction liquid was left cooled, and dropwise put into ethanol/water(250 ml/50 ml) to give a crude end-capped polymer 10.

The crude end-capped polymer 10 was dissolved in toluene, andreprecipitated in acetone, and the formed polymer was collected throughfiltration. The resulting polymer was dissolved in toluene, washed withdiluted hydrochloric acid, and reprecipitated in ammonia-containingethanol. The polymer collected through filtration was purified throughcolumn chromatography to give the intended polymer 10 (0.9 g). Theweight-average molecular weight and the number-average molecular weightof the polymer 10 were measured, and were as follows:

Weight-Average Molecular Weight (Ms)=60000

Number-Average Molecular Weight (Mn)=27000

Dispersity (Mw/Mn)=2.2

Production Examples 43 to 47

Intended polymers, arylamine polymers 11 to 15 were produced accordingto the production method of Production Example 42 but changing themonomers to the compounds shown in Table 2 below. The thus-obtainedpolymers are shown in Table 2.

TABLE 2 Amount of Fluoren- Amount of Amount of PE. Po. amine Ar^(a1)Br—Ar^(a1)—Br Ar^(a2) Ar^(a2)—NH₂ 42 10  7.50 g

 3.52 g

 0.22 g 43 11 3.320 g

1.560 g

 0.100 g 44 12  1.16 g

 0.55 g

0.0404 g 45 13 1.645 g

0.748 g

 0.057 g 46 14  2.02 g

 0.92 g

 0.073 g 47 15 1.852 g

0.874 g

0.0589 g Amount of Yield of Mw/ PE. Ar^(a3) Br—Ar^(a3)—Br i j k PolymerMw Mn Mn 42

 3.82 g 0.475 0.025 0.475  0.9 g 60000 27000 2.2 43

2.462 g 0.475 0.475 0.025 0.208 g 46000 17000 2.7 44

 0.86 g 0.47  0.03  0.47   0.73 g 52000 24700 2.1 45

 1.22 g 0.471 0.029 0.471  1.24 g 56500 34900 1.6 46

 1.50 g 0.471 0.029 0.471  1.86 g 76100 34600 2.2 47

1.089 g 0.47  0.03  0.47   0.83 g 84400 55900 1.5 PE.: “ProductionExample” Po.: “Polymer”

Production Examples 48 to 58

Intended polymers, various arylamine polymers 16 to 26 were produced inthe same manner as in the production methods of Production Examples 35and 42, for which, however, monomers as in the following reactionformula were reacted according to the following reaction formula andTable 3. The obtained polymers are shown in Table 3.

TABLE 3 Amount of Fluoren- Amount of PE PO amine Ar^(a1) Br—Ar^(a1)—BrAr^(a2) 48 16 2.630 g

2.500 g

49 17 1.754 g

3.000 g

50 18  1.68 g

 3.0 g

51 19 2.065 g

3.493 g

52 20 2.241 g

 4.0 g

53 21 1.153 g

 2.0 g

54 22 1.086 g

1.774 g

55 23 1.185 g

1.950 g

56 24  1.90 g

 1.57 g  0.98 g

57 25 0.918 g

 1.5 g

58 26 2.097 g

3.538 g

Amount of Amount of Yield of PE Ar^(a2)—NH₂ Ar^(a4) Ar^(a4)—NH₂ i jPolymer Mw Mn Mw/Mn 48  0.047 g

 0.047 g 0.94 0.03   0.9 g  31300 15100 2.1 49  0.299 g

 0.335 g 0.51 0.10   0.7 g  26200 15000 1.7 50  0.19 g

 0.36 g 0.5  0.1   1.71 g  46800 20100 2.3 51  0.178 g

 0.231 g 0.66 0.131  0.7 g  31700 21100 1.5 52  0.250 g

 0.478 g 0.5  0.1   2.7 g  57000 30000 1.9 53  0.050 g

 0.149 g 0.64 0.05   0.5 g  29000 12600 2.3 54  0.184 g

 0.197 g 0.54 0.105  2.2 g  27300 14400 1.9 55 0.1087 g

0.0690 g 0.83 0.086  1.63 g 332300 36300 9.2 56  0.148 g

 0.094 g 0.85 0.075  1.6 g 137000 53000 2.6 57 0.1026 g

0.0074 g 0.81 0.16   0.54 g  42000 20400 2.1 58  0.880 g

 0.418 g 0.4  0.301 0.476 g  23100 13500 1.7 PE: “Production Example”.PO: “Polymer”

Production Example 59

An intended polymer, arylamine polymer 27 was produced in the samemanner as in the production methods of Production Examples 35 and 42,for which, however, monomers as in the following reaction formula werereacted according to the following reaction formula and Table 4. Theobtained polymer is shown in Table 4.

TABLE 4 Production Amount of Example Polymer Ar^(a1) Br—Ar^(a1)—Br 59 27

0.185 g Production Example Amine 1 59

Amount Production of Example Amine 1 Amine 2 59 0.60 g

Production Amount of Yield of Example Amine 2 i Polymer Mw 59 0.03 g0.9387 0.41 g 70000

Production Examples 60 to 64)

Intended polymers 28 to 32 were produced in the same manner as in theproduction methods of Production Examples 35 and 42, for which, however,monomers as in the following reaction formula were reacted according tothe following reaction formula and Table 5. The obtained polymers areshown in Table 5.

TABLE 5 Production Amount of Example Polymer Ar^(a1) Br—Ar^(a1)—BrAr^(a2) 60 28

7.05 g

61 29

2.82 g

62 30

2.32 g

63 31

2.08 g

64 32

3.59 g

Production Amount of Amount of Example Ar^(a2)NH₂ Ar^(a3) Ar^(a3)NH₂ nYield Mw Mn Mw/Mn 60 3.71 g

0.90 g 0.8    0.7 g 63900 40300 1.6 61 1.80 g

0.09 g 0.95  0.37 g 46500 28300 1.6 62 1.49 g

0.54 g 0.7234 0.61 g 28000 16600 1.7 63 0.30 g

0.04 g 0.9442 0.90 g 72300 35500 2.0 64 0.95 g

0.13 g 0.9409 3.59 g 67900 35400 1.9[Production of Comparative Polymers]

Comparative Production Example 1

In a nitrogen flow, aqueous 20% tetraethylammonium hydroxide solution(11 ml) was added to a toluene (59 ml) solution of the compound 4 (3.26g), the compound 6 (0.45 g), the product 4 (1.530 g;1,8-dibromopyrene/1,6-dibromopyrene=33/67) and the compound 5 (1.34 g),and tetrakis(triphenylphosphine)palladium(0) (0.075 g) was addedthereto, and stirred for 6 hours with heating under heat. After leftcooled, the reaction liquid was added to methanol, the precipitatedcrude polymer was collected through filtration and dried. In a nitrogenflow, aqueous 20% tetraethylammonium hydroxide solution (24 ml) wasadded to a solution of the resulting crude polymer, bromobenzene (0.20g) and toluene (100 ml), and tetrakis(triphenylphosphine)palladium(0)(0.451 g) was added thereto, and stirred for 2 hours with heating underheat. Subsequently, phenylboronic acid (1.80 g) was added to it, andstirred for 6 hours with heating under heat. After left cooled, thereaction liquid was added to ethanol, the precipitated crude polymer wascollected through filtration, dried, and purified through silica gelcolumn with a developing solvent of toluene and tetrahydrofuran. Fromthe tetrahydrofuran solution, the product was reprecipitated in ethanol,collected through filtration and dried to give a comparative polymer 1(1.45 g).

Weight-Average Molecular Weight (Ms)=22,000

Number-Average Molecular Weight (Mn)=14,000

Comparative Production Example 2

In a nitrogen flow, the compound 1 (10.0 g), bis(pinacolato)diborane(10.8 g), potassium acetate (10.13 g) and dimethyl sulfoxide (150 ml)were put in a reactor, heated up to 60° C., stirred for 30 minutes, and(bisdiphenylphosphinoferrocene)dichloropalladium complex was added to itand reacted at 80° C. for 6 hours. After the reaction, this was leftcooled to room temperature, and toluene (100 ml) and water (120 ml) wereadded to the reaction liquid, stirred, processed for liquid-liquidseparation, and the aqueous layer was extracted with toluene. Theorganic layers were combined, dried with magnesium sulfate, andconcentrated. The resulting crude product was purified through silicagel column chromatography (n-hexane/ethyl acetate) to give the intendedproduct 33 (7.9 g).

In a nitrogen flow, the product 33 (7.9 g), 3-bromoaniline (3.47 g),toluene/ethanol (60 ml/30 ml) and aqueous 2 M sodium carbonate solution(20 ml) were put in a reactor, stirred for 30 minutes under heat at 60°C., the system was degassed, and tetrakis(triphenylphosphine)palladium(0.7 g) was added thereto and refluxed for 6 hours. After left cooled toroom temperature, toluene (100 ml) and water (120 ml) were added to thereaction liquid, stirred, processed for liquid-liquid separation, andthe aqueous layer was extracted with toluene. The organic layers werecombined, dried with magnesium sulfate, and concentrated. The resultingcrude product was purified through silica gel column chromatography(n-hexane/ethyl acetate) to give the intended product 34 (3.8 g).

4-N-octylaniline (2.285 g, 11.13 mmol), the product 34 (0.2 g, 0.59mmol), 4,4′-dibromobiphenyl (1.83 g, 5.86 mmol), sodium tert-butoxide(3.6 g, 37.49 mmol), and toluene (20 ml) were put in a reactor, and thesystem was fully purged with nitrogen and heated up to 50° C. (solutionA). Tri-t-butyl phosphine (0.189 g, 0.94 mmol) was added to a toluene(10 ml) solution of tris(dibenzylideneacetone)dipalladium/chloroformcomplex (0.12 g, 0.12 mmol), and heated up to 50° C. (solution B). In anitrogen flow, the solution B was added to the solution A, and reactedfor 1 hour with heating under reflux. The absence of the startingmaterials was confirmed, and 4,4′-dibromobiphenyl (1.72 g, 5.51 mmol)was additionally added to it. After this was heated under reflux for 1hour, the start of polymerization was confirmed; and4,4′-dibromobiphenyl (0.036 g, 0.12 mmol) was additionally added to itat intervals of 40 minutes for a total of 3 times (0.11 g in total).After the total amount of 4,4′-dibromobiphenyl was added, this wasfurther heated under reflux for 1 hour, and the reaction liquid was leftcooled, and dropwise put into methanol (300 ml) to give a crudecomparative polymer 2 through crystallization.

The resulting crude comparative polymer 2 was dissolved in toluene (110ml), and bromobenzene (0.39 g, 2.48 mmol) and sodium tert-butoxide (3.8g, 39.74 mmol) were added thereto, then the system was fully purged withnitrogen, and heated up to 50° C. (solution C). Tri-t-butyl phosphine(0.2 g, 0.99 mmol) was added to a toluene (10 ml) solution oftris(dibenzylideneacetone)dipalladium/chloroform complex (0.13 g, 0.12mmol), and heated up to 50° C. (solution D). In a nitrogen flow, thesolution D was added to the solution C, and reacted for 2 hours withheating under reflux. A toluene (2 ml) solution of N,N-diphenylamine(2.1 g, 12.4 mmol) was added to the reaction liquid, and further reactedfor 6 hours with heating under reflux. The reaction liquid was leftcooled, and dropwise put into ethanol/water (250 ml/50 ml) to give acrude comparative polymer 2 of which the terminal residues were capped.

The crude end-capped comparative polymer 2 was dissolved in toluene, andreprecipitated in acetone, and the formed polymer was collected throughfiltration. The resulting polymer was dissolved in toluene, washed withdiluted hydrochloric acid, and reprecipitated in ammonia-containingethanol. The polymer collected through filtration was purified throughcolumn chromatography to give the intended comparative polymer 2 (0.84g).

Weight-Average Molecular Weight (Ms)=51600

Number-Average Molecular Weight (Mn)=26500

Dispersity (Mw/Mn)=1.95

Comparative Production Example 3

The compound 7 (10.09 g), the compound 6 (2.08 g),2,7-dibromo-9,9′-dihexylfluorene (12.85 g), sodium tert-butoxide (9.23g) and toluene (70 ml) were put in a reactor, and the system was fullypurged with nitrogen and heated up to 60° C. (solution A). Tri-t-butylphosphine (0.24 g) was added to a toluene (5 ml) solution oftris(dibenzylideneacetone)dipalladium/chloroform complex (0.16 g), andheated up to 60° C. (solution B). In a nitrogen flow, the solution B wasadded to the solution A, and reacted for 1 hour with heating underreflux. 2,7-Dibromo-9,9-dihexylfluorene (0.15 g) was further added to itat intervals of 30 minutes for a total of 3 times. Further, this washeated under reflux, then the reaction liquid was left cooled, anddropwise put into ethanol to precipitate a crude comparative polymer 3.

The resulting crude comparative polymer 3 was dissolved in toluene (290ml), and bromobenzene (0.94 g) and sodium tert-butoxide (4.32 g) wereadded thereto, then the system was fully purged with nitrogen, andheated up to 60° C. (solution C). Tri-t-butyl phosphine (0.24 g) wasadded to a toluene (10 ml) solution oftris(dibenzylideneacetone)dipalladium/chloroform complex (0.16 g), andheated up to 60° C. (solution D). In a nitrogen flow, the solution D wasadded to the solution C, and reacted for 2 hours with heating underreflux. A toluene (10 ml) solution of N,N-diphenylamine (5.08 g) wasadded to the reaction liquid, and further reacted for 4 hours withheating under reflux. The reaction liquid was left cooled, and dropwiseput into ethanol to give a crude comparative polymer 3 of which theterminal residues were capped.

The crude end-capped comparative polymer 3 was dissolved in toluene, andreprecipitated in acetone, and the formed polymer was collected throughfiltration. The resulting polymer was dissolved in toluene, washed withdiluted hydrochloric acid, and reprecipitated in ammonia-containingethanol. The polymer collected through filtration was purified throughcolumn chromatography to give the intended comparative polymer 3 (11.27g).

Weight-Average Molecular Weight (Ms)=47500

Number-Average Molecular Weight (Mn)=23700

Dispersity (Mw/Mn)=2.00

Comparative Production Example 4

In a nitrogen flow, aqueous 20% tetraethylammonium hydroxide solution(25 ml) was added to a toluene (50 ml) solution of the compound 4 (3.57g), the compound (2.61 g) and the compound 8 (0.61 g), andtetrakis(triphenylphosphine)palladium(0) (0.06 g) was added to it andstirred for 4 hours with heating under reflux. After left cooled, thereaction liquid was added to ethanol, and the precipitated crude polymerwas collected through filtration and dried. In a nitrogen flow, aqueous20% tetraethylammonium hydroxide solution (40 ml) was added to asolution of the resulting polymer, bromobenzene (0.22 g) and toluene(100 ml), and tetrakis(triphenylphosphine)palladium(0) (0.06 g) wasadded to it and stirred for 2 hours with heating under reflux.Subsequently, phenylboronic acid (0.87 g) was added thereto and stirredfor 6 hours with heating under reflux. After left cooled, the reactionliquid was added to ethanol, the precipitated crude comparative polymer4 was collected through filtration, dried, and purified through silicagel column with a developing solvent of toluene and tetrahydrofuran. Theproduct was reprecipitated from the tetrahydrofuran solution in ethanol,collected through filtration and dried to give the comparative polymer 4(2.80 g).

Weight-Average Molecular Weight (Ms)=41400

Number-Average Molecular Weight (Mn)=22600

Dispersity (Mw/Mn)=1.83

[Construction of Organic Electroluminescence Element]

Example 1

An organic electroluminescence element shown in FIG. 1 was constructed.

On a glass substrate 1 having, as deposited thereon, an indium tin oxide(ITO) transparent conductive film having a thickness of 120 nm (SanyoVacuum Industries' sputtered product), an anode 2 was formed bypatterning thereon to be a stripe having a width of 2 mm, according toordinary photolithography combined with hydrochloric acid etching. Thethus-patterned ITO substrate was ultrasonically washed with an aqueoussurfactant solution, washed with ultrapure water, ultrasonically washedwith ultrapure water, and washed with ultrapure water in that order,then dried with compressed air, and finally washed with UV/ozone.

First, a coating liquid for forming hole injection layer was prepared,comprising a hole-transporting polymer material represented by thefollowing structural formula (P1) (weight-average molecular weight,26500; number-average molecular weight, 12000),4-isopropyl-4′-methyldiphenyliodonium tetrakis(pentafluorophenyl)boraterepresented by the following structural formula (A1) and ethyl benzoate.The coating liquid was applied onto the anode 2 in a mode of spincoating, thereby forming a hole injection layer 3 having a thickness of30 nm.

[Chemical Formula 97]

<Coating Liquid for Forming Hole Injection Layer> Solvent ethyl benzoateCoating liquid concentration P1: 2.0% by weight A1: 0.8% by weight

<Condition for Forming Hole Injection Layer 3> Number of spinnerrotations 1500 rpm Spinner rotation time 30 seconds Spin coatingatmosphere in air Heating condition in air, 230° C., 3 hours

Subsequently, a composition for organic electroluminescence elementcontaining a polymer compound (i) of the invention represented by thefollowing structural formula (H1) (the polymer 1 obtained in ProductionExample 33) was prepared, and this was applied in a mode of spin coatingunder the condition mentioned below, and crosslinked by heating to forma hole transport layer 4 having a thickness of 22 mm.

[Chemical Formula 98]

<Coating Liquid for Forming Hole Transport Layer> Solvent toluene Solidconcentration 0.4% by weight

<Condition for Forming Hole Transport Layer 4> Number of spinnerrotations 1500 rpm Spinner rotation time 30 seconds Spin coatingatmosphere in nitrogen Heating condition in nitrogen, 230° C., 1 hour

The substrate with the hole injection layer 3 and the hole transportlayer 4 formed thereon was transferred into a vacuum deposition chamber,the chamber was roughly degassed via an oil-sealed rotary pump, and thenfurther degassed so that the vacuum degree inside the chamber couldreach 1.3×10⁻⁴ Pa or less via a cryopump; and a film comprising acompound having the following structural formula (E4) and an iridiumcomplex (D2) shown below was formed thereon according to a vacuumevaporation method to form a light emission layer 5. The light emissionlayer 5 having a thickness of 32 nm was thus formed with the vapordeposition rate of (E4) controlled to be 0.5 angstrom/second and thevapor deposition rate of the iridium complex (D2) to be 0.03angstrom/second.

Next, a compound (E3) having the following structural formula waslaminated on it according to a vacuum evaporation method to form a holeinhibition layer 6. The hole inhibition layer 6 having a thickness of 10nm was thus formed, as laminated on the light emission layer 5, with thevapor deposition rate controlled to be from 0.7 to 1.2 angstrom/second.

Subsequently, tris(8-hydroxyquinolinato)aluminium was heated andvapor-deposited to form an electron transport layer 7. In this case, thevapor deposition speed was controlled to be within a range of from 0.7to 1.3 angstroms/second, and the electron transport layer 7 having athickness of 30 nm was formed as laminated on the hole inhibition layer6.

The device processed for vapor deposition thereon up to the electrontransport layer 7 was once taken out from the vacuum deposition chamberinto air, and a 2-mm wide stripe shadow mask for cathode deposition wasstuck to the device in such a manner that the mask could be inperpendicular to the ITO stripe of the anode 2, and the device was putin a different vacuum deposition chamber, and similarly the chamber wasdegassed to a vacuum degree of at most 1.3×10-4 Pa.

Using a molybdenum boat, lithium fluoride (LiF) was vapor-deposited onthe electron transport layer 7 at a controlled vapor deposition speedfalling within a range of from 0.08 to 0.13 angstrom/second, therebyforming thereon an electron injection layer 8 having a thickness of 0.5nm. Next, similarly to the above, aluminium was heated on a molybdenumboat and vapor-deposited at a deposition speed falling within a range offrom 0.5 to 6.0 angstrom/sec, thereby forming an aluminium layer havinga thickness of 80 nm as a cathode 9. In forming the above two layers,the substrate temperature was room temperature.

Subsequently, the device was sealed up according to the method mentionedbelow, for preventing the device from being degraded by moisture in airduring storage.

In the nitrogen globe box connected to the vacuum deposition chamber, aphotocurable resin 30Y-437 (by Three Bond) was applied to the outerperiphery of a glass sheet having a size of 23 mm×23 mm, to a width ofabout 1 mm, and a moisture getter sheet (by Dynic) was arranged in thecenter part. The substrate after cathode formation thereon was put on itand stuck thereto in such a manner that the coated side of the substratecould face the desiccant sheet. Subsequently, the area coated with thephotocurable resin was irradiated with UV rays and the resin was therebycured.

In the manner as above, an organic electroluminescence element having alight emission area part with a size of 2 mm×2 mm was obtained. Thelight emission characteristics of the device are as follows:

Brightness/current: 17.2 [cd/A] @ 100 cd/m²

Voltage: 5.5 [V] @ 100 cd/m²

Current efficiency: 9.7 [lm/W] @ 100 cd/m²

The maximum wavelength of the light emission spectrum of the device was516 nm, and this was identified as one from the iridium complex (D2).The chromaticity was CIE (x, y)=(0.311, 0.622).

The light emission characteristics and the lifetime of the device areshown in Table 1. The drive lifetime indicates the brightness half-valueperiod at an initial brightness of 2500 cd/m² in room temperaturedriving.

As shown in Table 6, it is known that the organic electroluminescenceelement constructed by the use of the polymer compound of the inventionhas a low drive voltage, a high current efficiency and a long drivelifetime.

Comparative Example 1

An organic electroluminescence element shown in FIG. 1 was constructedin the same manner as in Example 1, for which, however, the polymercompound (i) having the structural formula (H1) of the invention waschanged to a polymer compound represented by the following structuralformula (H2) (comparative polymer 1 produced in Comparative ProductionExample 1) in forming the hole transport layer 4. In this, the thicknessof the hole transport layer was 20 nm.

In the manner as above, an organic electroluminescence element having alight emission area part with a size of 2 mm×2 mm was obtained. Thelight emission characteristics of the device are as follows:

Brightness/current: 18.5 [cd/A] @ 100 cd/m²

Voltage: 6.1 [V] @ 100 cd/m²

Current efficiency: 9.5 [lm/W] @ 100 cd/m²

The maximum wavelength of the light emission spectrum of the device was516 nm, and this was identified as one from the iridium complex (D2).The chromaticity was CIE (x, y)=(0.311, 0.622).

The brightness half-value period at an initial brightness of 2500 cd/m²in room temperature driving of the thus-obtained organicelectroluminescence element is shown below.

TABLE 6 Current Standardized Drive Efficiency Lifetime relative Voltage[V] [lm/W] to 1 of @ 100 cd/m² @ 100 cd/m² Comparative Example 1 Example1 5.5 9.7 1.1 Comparative 6.1 9.5 1.0 Example 1

Example 2

An organic electroluminescence element shown in FIG. 1 was constructedin the same manner as in Example 1, for which, however, the polymercompound (i) having the structural formula (H1) of the invention waschanged to a polymer compound of the invention represented by thefollowing structural formula (H3) (polymer 32 produced in ProductionExample 64) in forming the hole transport layer 4. In this, thethickness of the hole transport layer was 20 nm.

The light emission characteristics of the obtained device are asfollows:

Brightness/current: 13.4 [cd/A] @ 100 cd/m²

Voltage: 5.3 [V] @ 100 cd/m²

Current efficiency: 7.5 [lm/W] @ 100 cd/m²

Comparative Example 2

An organic electroluminescence element shown in FIG. 1 was constructedin the same manner as in Example 1, for which, however, the polymercompound (i) having the structural formula (H1) of the invention waschanged to a polymer compound represented by the following structuralformula (H4) (comparative polymer 9 produced in Comparative ProductionExample 9) in forming the hole transport layer 4. In this, the thicknessof the hole transport layer was 20 nm.

The light emission characteristics of the obtained device are asfollows:

Brightness/current: 17.1 [cd/A] @ 100 cd/m²

Voltage: 5.5 [V] @ 100 cd/m²

Current efficiency: 9.7 [lm/W] @ 100 cd/m²

The voltage and the current efficiency at 100 cd/m², and the drivelifetime at an initial brightness of 2,500 cd/m², as standardizedrelative to the value in Comparative Example 2, of the organicelectroluminescence elements obtained in Example 2 and ComparativeExample 2 are shown in Table 7.

TABLE 7 Standardized Drive Lifetime relative Voltage [V] to 1 of @ 100cd/m² Comparative Example 2 Example 2 5.3 1.1 Comparative 5.5 1.0Example 2

As shown in Table 7, it is known that the organic electroluminescenceelement constructed by the use of the polymer compound of the inventionhas a low drive voltage and a long drive lifetime.

Example 3

An organic electroluminescence element was constructed in the samemanner as in Example 2, for which, however, the light emission layer 5was formed as follows:

A composition for organic electroluminescence element was prepared,comprising a compound represented by the following structural formula(E5) and a compound represented by the following structural formula(D3); and this was formed into a film according to spin coating underthe condition mentioned below, and heated to give a light emission layer5 having a thickness of 40 nm.

[Chemical Formula 104]

<Coating Liquid for Forming Light Emission Layer> Solvent tolueneCoating liquid concentration (E5) 0.80% by weight (D3) 0.08% by weight

<Condition for Forming Light Emission Layer> Number of spinner rotations1500 rpm Spinner rotation time 30 seconds Spin coating atmosphere innitrogen Heating condition 130° C., 1 hour, under reduced pressure (0.1MPa)

The light emission characteristics of the obtained device are asfollows:

Brightness/current: 4.3 [cd/A] @ 1,000 cd/m²

Voltage: 8.1 [V] @ 1,000 cd/m²

Example 4

An organic electroluminescence element shown in FIG. 1 was constructedin the same manner as in Example 3, for which, however, the polymercompound having the structural formula (H3) of the invention was changedto a polymer compound of the invention represented by the followingstructural formula (H5) (polymer 2 produced in Production Example 34) informing the hole transport layer 4. In this, the thickness of the holetransport layer was 20 nm.

The light emission characteristics of the obtained device are asfollows:

Brightness/current: 2.7 [cd/A] @ 1,000 cd/m²

Voltage: 6.6 [V] @ 1,000 cd/m²

Example 5

An organic electroluminescence element shown in FIG. 1 was constructedin the same manner as in Example 3, for which, however, the polymercompound having the structural formula (H3) of the invention was changedto a polymer compound (ii) of the invention represented by the followingstructural formula (H6) (polymer 12 produced in Production Example 44)in forming the hole transport layer 4. In this, the thickness of thehole transport layer was 20 nm.

The light emission characteristics of the obtained device are asfollows:

Brightness/current: 3.9 [cd/A] @ 1,000 cd/m²

Voltage: 6.9 [V] @ 1,000 cd/m²

Example 6

An organic electroluminescence element shown in FIG. 1 was constructedin the same manner as in Example 3, for which, however, the polymercompound having the structural formula (H3) of the invention was changedto a polymer compound (ii) of the invention represented by the followingstructural formula (H7) (polymer 24 produced in Production Example 56)in forming the hole transport layer 4. In this, the thickness of thehole transport layer was 20 nm.

The light emission characteristics of the obtained device are asfollows:

Brightness/current: 4.0 [cd/A] @ 1,000 cd/m²

Voltage: 7.7 [V] @ 1,000 cd/m²

Example 7

An organic electroluminescence element shown in FIG. 1 was constructedin the same manner as in Example 3, for which, however, the polymercompound having the structural formula (H3) of the invention was changedto a polymer compound (ii) of the invention represented by the followingstructural formula (H8) (polymer 31 produced in Production Example 63)in forming the hole transport layer 4. In this, the thickness of thehole transport layer was 20 nm.

The light emission characteristics of the obtained device are asfollows:

Brightness/current: 3.7 [cd/A] @ 1,000 cd/m²

Voltage: 8.1 [V] @ 1,000 cd/m²

Example 8

An organic electroluminescence element shown in FIG. 1 was constructedin the same manner as in Example 3, for which, however, the polymercompound having the structural formula (H3) of the invention was changedto a polymer compound (ii) of the invention represented by the followingstructural formula (H9) (polymer 8 produced in Production Example 40) informing the hole transport layer 4. In this, the thickness of the holetransport layer was 20 nm.

The light emission characteristics of the obtained device are asfollows:

Brightness/current: 3.8 [cd/A] @ 1,000 cd/m²

Voltage: 7.2 [V] @ 1,000 cd/m²

Comparative Example 3

An organic electroluminescence element shown in FIG. 1 was constructedin the same manner as in Example 3, for which, however, the polymercompound having the structural formula (H3) of the invention was changedto a polymer compound represented by the following structural formula(H10) (comparative polymer 3 produced in Comparative Production Example3) in forming the hole transport layer 4. In this, the thickness of thehole transport layer was 20 nm.

The light emission characteristics of the obtained device are asfollows:

Brightness/current: 2.9 [cd/A] @ 1,000 cd/m²

Voltage: 8.5 [V] @ 1,000 cd/m²

The voltage and the current efficiency at 1,000 cd/m², and the drivelifetime at an initial brightness of 1,000 cd/m², as standardizedrelative to the value in Comparative Example 3, of the organicelectroluminescence elements obtained in Examples 3 to 8 and ComparativeExample 3 are shown in Table 8.

TABLE 8 Current Standardized Drive Efficiency Lifetime relative Voltage[V] [cd/A] to 1 of @ 1,000 cd/m² @ 1,000 cd/m² Comparative Example 3Example 3 8.1 4.3 2.0 Example 4 6.6 2.7 2.4 Example 5 6.9 3.9 1.5Example 6 7.7 4.0 1.5 Example 7 8.1 3.7 1.5 Example 8 7.2 3.8 1.4Comparative 8.5 2.9 1.0 Example 3

As shown in Table 8, it is known that the organic electroluminescenceelements constructed by the use of the polymer compound of the inventionhave a low drive voltage, a high current efficiency and a long drivelifetime.

Example 9

An organic electroluminescence element was constructed in the samemanner as in Example 3, for which, however, the hole transport layer 4and the light emission layer 5 were formed in the manner mentionedbelow.

(Formation of Hole Transport Layer 4)

A hole transport layer having a thickness of 20 nm was formed in thesame manner as in Example 3, for which, however, the polymer compoundhaving the structural formula (H3) of the invention to form the holetransport layer 4 in Example 3 was changed to a polymer compound (ii) ofthe invention represented by the following structural formula (H11)(polymer 29 produced in Production Example 61).

(Formation of Light Emission Layer)

A light emission layer 5 having a thickness of 47 nm was formed in thesame manner as in Example 3, for which, however, the compound of theabove formula (E5) was changed to a compound represented by thefollowing structural formula (E6) and the composition of the lightemission layer-forming coating liquid was changed as follows:

[Chemical Formula 112]

<Coating Liquid for Forming Light Emission Layer> SolventCyclohexylbenzene Coating Liquid Concentration E6: 2.30% by weight D3:0.23% by weight

In the manner as above, an organic electroluminescence element having alight emission area part with a size of 2 mm×2 mm was obtained. Thelight emission characteristics of the device are as follows:

Brightness/current: 2.5 [cd/A] @ 100 cd/m²

The maximum wavelength of the light emission spectrum of the device was464 nm, and this was identified as one from the compound (D1). Thechromaticity was CIE (x, y)=(0.142, 0.161).

Comparative Example 4

An organic electroluminescence element shown in FIG. 1 was constructedin the same manner as in Example 9, for which, however, the polymercompound (ii) having the structural formula (H11) of the invention waschanged to a polymer compound represented by the following structuralformula (H12) (comparative polymer 2 produced in Comparative ProductionExample 2) in forming the hole transport layer 4. In this, the thicknessof the hole transport layer was 20 nm.

The light emission characteristics of the thus-constructed organicelectroluminescence element having a light emission area part with asize of 2 mm×2 mm are as follows:

Brightness/current: 2.1 [cd/A] @ 100 cd/m²

The maximum wavelength of the light emission spectrum of the device was464 nm, and this was identified as one from the compound (D1). Thechromaticity was CIE (x, y)=(0.143, 0.173).

The current efficiency at 100 cd/m² of the organic electroluminescenceelements obtained in Example 9 and Comparative Example 4 is shown inTable 9.

TABLE 9 Current Efficiency [cd/A] @ 100 cd/m² Example 9 2.5 Comparative2.1 Example 4

As shown in Table 9, the device constructed by the use of the polymercompound of the invention has a high current efficiency.

While the invention has been described in detail and with reference tospecific embodiments thereof, it will be apparent to one skilled in theart that various changes and modifications can be made therein withoutdeparting from the spirit and scope thereof.

The present application is based on a Japanese patent application filedApr. 2, 2008 (Japanese Patent Application No. 2008-096522), and thecontents thereof are hereby incorporated by reference.

INDUSTRIAL APPLICABILITY

The polymer compound of the invention is favorably used in variousfields where organic EL devices are used, for example, in the device offlat panels and displays (for example, for OA computers and wall-mountedtelevisions), light sources taking advantage of surface-emitting devices(for example, light sources for duplicators, backlight sources forliquid-crystal displays and meter gauges), sign boards, sign lamps, etc.

As having substantially excellent oxidation-reduction resistantstability, the polymer compound of the invention is useful not only fororganic electroluminescence elements but also for general organicdevices such as electrophotographic photoreceptors, organic solar cells,etc.

DESCRIPTION OF REFERENCE NUMERALS

-   1 Substrate-   2 Anode-   3 Hole injection Layer-   4 Hole Transport Layer-   5 Light Emission Layer-   6 Hole Inhibition Layer-   7 Electron Transport Layer-   8 Electron Injection Layer-   9 Cathode

The invention claimed is:
 1. A polymer compound comprising a repeatingunit represented by the following formula (II):

wherein p indicates an integer of from 0 to 3; Ar²¹ and Ar²² eachindependently represent a direct bond, an aromatic hydrocarbon groupoptionally having a substituent, or an aromatic heterocyclic groupoptionally having a substituent; Ar²³ to Ar²⁵ each independentlyrepresent an aromatic hydrocarbon group optionally having a substituent,or an aromatic heterocyclic group optionally having a substituent; T²represents a group containing a group represented by the followingformula (IV); provided that Ar²¹ and Ar²² are not direct bonds at thesame time; further, when Ar²¹, Ar²² and Ar²⁴ are fluorene ringsoptionally having a substituent, said fluorine ring does not have agroup containing a crosslinking group as the substituent; thecross-linking group is any of the groups selected from the followinggroup of cross-linking groups;

wherein in R²¹ to R²⁵ each independently represent a hydrogen atom or analkyl group, Ar⁴¹ represents an aromatic hydrocarbon group optionallyhaving a substituent, or an aromatic heterocyclic group optionallyhaving a substituent, the benzocyclobutene ring may have a substituent,and the substituents may together form a ring,

wherein the benzocyclobutene ring in the formula (IV) may have asubstituent; and the substituents may bond to each other to form a ring.2. The polymer compound as claimed in claim 1, further comprising arepeating unit represented by the following formula (II′):

wherein q indicates an integer of from 0 to 3; Ar³¹ and Ar³² eachindependently represent a direct bond, an aromatic hydrocarbon groupoptionally having a substituent, or an aromatic heterocyclic groupoptionally having a substituent, Ar³³ to Ar³⁵ each independentlyrepresent an aromatic hydrocarbon group optionally having a substituent,an aromatic heterocyclic group optionally having a substituent; providedthat Ar³¹ and Ar³² are not direct bonds at the same time; Ar³¹ to Ar³⁵do not have a group containing a group of the formula (IV) as thesubstituent; further, when Ar³¹, Ar³² and Ar³⁴ are fluorene ringsoptionally having a substituent, said fluorine ring does not have agroup containing a crosslinking group as the substituent; wherein thecross-linking group is any of the groups selected from the followinggroup of cross-linking groups;

wherein in R²¹ to R²⁵ each independently represent a hydrogen atom or analkyl group, Ar⁴¹ represents an aromatic hydrocarbon group optionallyhaving a substituent, or an aromatic heterocyclic group optionallyhaving a substituent, the benzocyclobutene ring may have a substituent,and the substituents may together form a ring.
 3. A net-like polymercompound produced by crosslinking the polymer compound of claim
 1. 4. Acomposition for organic electroluminescence element, containing thepolymer compound of claim
 1. 5. An organic electroluminescence elementcomprising, on a substrate, an anode, a cathode and an organic layerbetween the anode and the cathode, wherein the organic layer comprises alayer containing the net-like polymer compound of claim
 3. 6. Theorganic electroluminescence element as claimed in claim 5, wherein thelayer containing the net-like polymer compound is a hole injection layeror a hole transport layer.
 7. The organic electroluminescence element asclaimed in claim 5; wherein the organic layer comprises a hole injectionlayer, a hole transport layer and a light emission layer, and all of thehole injection layer, the hole transport layer and the light emissionlayer are formed according to a wet film formation method.
 8. An organicEL display, comprising the organic electroluminescence element of claim5.
 9. An organic EL lighting, comprising the organic electroluminescenceelement of claim
 5. 10. A polymer compound comprising at least onerepeating unit selected from a group of the following repeating units A,and at least one repeating unit selected from a group of the followingrepeating units B: <Group of Repeating Units A>